Fullerene-containing hemicarceplexes and a method of purifying fullerenes by using the same

ABSTRACT

Fullerene⊙CTV complexes, comprising fullerene⊙CTV hemicarceplexes, formed by various cyclotriveratrylene (CTV)-based molecular cages and various fullerene guests are disclosed. A method of direct isolating at least a fullerene from fullerene mixtures by using the above fullerene CTV hemicarceplexes but without using crystallization or HPLC is also disclosed.

CROSS-REFERENCE TO RELATED APPLICATION

This application is a continuation-in-part of U.S. application Ser. No.13/653,539, filed Oct. 17, 2012, the full disclosure of which isincorporated herein by reference.

BACKGROUND

1. Technical Field

The disclosure relates to several fullerene-containing hemicarceplexesand a method of purifying fullerenes by using the same.

2. Description of Related Art

Because of their versatile configurations and attractive properties,fullerenes, including cylindrical carbon nanotubes (CNTs) and sphericaland spheroidal buckyballs, have found applications in a wide range offields, including materials science, chemistry, super- andsemi-conducting physics, and biology. Ignoring CNTs, which lack uniformdiameters or lengths, the most abundant structurally distinct species ina typical fullerene extract are two buckyballs, i.e. C₆₀ and C₇₀. Eventhough they have been investigated widely since their discovery in the1980s, the practical applications of buckyballs have been limited bytheir poor solubilities in organic solvents; this characteristic hasalso seriously complicated their isolation and purification.

Several elegant methods have been developed for the isolation of themore-abundant C₆₀ from fullerene extracts; in contrast, isolating thelower-in-symmetry and photovoltaically-more-interesting C₇₀ in highpurity from the same mixtures has been less straightforward. Indeed,tedious purification involving crystallization and/or high-performanceliquid chromatography (HPLC) is frequently required to obtainhigh-purity C₇₀, making it much less affordable than C₆₀ of the samequality; accordingly, relatively limited research has been undertaken todiscover and expand the practical applications of C₇₀.

One attractive approach for the selective isolation of C₇₀ involvesexploiting its host-guest complexation behavior. Although a fewjudiciously designed synthetic host molecules do form complexes with C₆₀and C₇₀ in solution, using such host-guest complexes as a means ofseparating mixtures of buckyballs (i.e., with high degrees ofselectivity and stability) remains a challenge.

Unlike carcerands, which cannot release their entrapped guests,hemicarcerands allow sequestration of complementary guests (forming roomtemperature-isolatable hemicarceplexes) as well as their release atelevated temperatures. Although Cram first proposed, in 1995, that theinternal space of a cavitand dimer might be a suitable host for C₆₀(Hemicarcerands with interiors potentially capable of binding largeguests. J. Chem. Soc., Chem. Commun. 1085-1087 (1995)), hemicarcerandsthat can selectively imprison guests as big as C₆₀ and C₇₀ have neverbeen realized previously, presumably because of difficulties inbalancing the steric sizes and free energies of complexation of the hostand guest components to allow selective sequestration and release of theguests.

SUMMARY

In one aspect, the present invention is directed to a fullerene⊙CTVcomplex, comprising a hemicarceplex, formed by trapping a fullereneguest or a derivative thereof (abbreviated as a guest molecule below) ina cyclotriveratrylene-based molecular cage (abbreviated as CTV below)having a chemical structure below, and LS1 and LS2 are first and secondlinking spacers respectively having a first chain length and a secondchain length, and the first chain length is shorter or equal to thesecond chain length. The first chain length of the first linking spacersdetermines an interior space of the CTV cage for accommodating the guestmolecule, and the second chain length of the second linking spacersdetermines an opening size of the CTV cage for entering the guestmolecule.

According to an embodiment, the first linking spacers or the secondlinking spacers are straight alkyl chains containing at least 10 carbonsfor accommodating a guest molecule having at least 60 atoms in the CTV.

According to another embodiment, the first linking spacers or the secondlinking spacers are straight alkyl chains containing 10-15 carbons foraccommodating the guest molecule having 60-84 carbons in the CTV.

For example, the cyclotriveratrylene-based molecular cage may be

According to another embodiment, at least one of the first and thesecond linking spacers containing a diester linkage. For example, thecyclotriveratrylene-based molecular cage may be

According to yet another embodiment, the complex may be C₆₀⊙CTV1,C₇₀⊙CTV1, C₇₆⊙CTV1, C₇₈⊙CTV1, C₇₀⊙CTV2, C₆₀⊙CTV2, C₆₀⊙CTV3,Sc₃N@C₈₀⊙CTV4, C₆₀⊙CTV5, C₇₀⊙CTV5, C₇₆⊙CTV5, C₇₈⊙CTV5, C₆₀⊙CTV6,C₇₀CTV7, C₇₆⊙CTV7, C₇₈⊙CTV7, C₈₂⊙CTV7, C₈₄⊙CTV7, C₈₆⊙CTV7, C₇₀CTV8,C₇₆⊙CTV8, C₇₈⊙CTV8, C₈₂⊙CTV8, C₈₄⊙CTV8, C₈₆⊙CTV8, C₇₀⊙CTV9, C₆₀⊙CTV11,or C₆₀⊙CTV12.

According to yet another embodiment, the complex may be C₇₀⊙CTV1,C₇₆⊙CTV1, C₇₈⊙CTV1, C₇₀⊙CTV2, C₆₀⊙CTV3, Sc₃N@C₈₀⊙CTV4, C₇₆⊙CTV5,C₇₈⊙CTV5, C₇₀⊙CTV7, C₇₆⊙CTV7, C₇₈⊙CTV7, C₈₂⊙CTV7, C₈₄⊙CTV7, C₈₆⊙CTV7,C₇₀⊙CTV8, C₇₆⊙CTV8, C₇₈⊙CTV8, C₈₂⊙CTV8, C₈₄⊙CTV8, C₈₆⊙CTV8, C₆₀⊙CTV11,or C₆₀⊙CTV12 when the complex is room temperature isolatable.

In another aspect, the present invention directs to a method of forminga fullerene⊙CTV hemicarceplex. The method comprises the following steps.A fullerene or a derivative thereof, and a cyclotriveratrylene-basedmolecular cage described above are mixed in a solvent to form a mixturesolution. Then, the mixture solution is heated to form a fullerene⊙CTVhemicarceplex.

According to an embodiment, the solvent can majorly contain CS₂, CH₂Cl₂,CHCl₃ or CHCl₂CHCl₂, for example.

In yet another aspect, the present invention directs to a method ofisolating at least a fullerene by using a fullerene⊙CTV hemicarceplex.The method comprises the following steps. First, a fullerene or aderivative thereof, and a cyclotriveratrylene-based molecular cagedescribed above are mixed in a first solvent to form a mixture solution.Next, the fullerene⊙CTV hemicarceplexe is isolated by columnchromatography without using crystallization or high performance liquidchromatography (HPLC). Then, the fullerene⊙CTV hemicarceplexe isdissociated in a second solvent.

According to an embodiment, the first solvent has less tendency than thefullerenes to occupy an inner space of the cyclotriveratrylene-basedmolecular cage. For example, the first solvent can majorly contain CS₂,CH₂Cl₂, CHCl₃, or CHCl₂CHCl₂.

According to another embodiment, the second solvent can dissolvefullerene⊙CTV hemicarceplex and allow its dissociation to releasefullerene. For example, the second solvent can majorly contain CS₂,CH₂Cl₂, CHCl₃, CHCl₂CHCl₂, benzene, toluene, or dichlorobenzene.

The forgoing presents a simplified summary of the disclosure in order toprovide a basic understanding to the reader. This summary is not anextensive overview of the disclosure and it does not identifykey/critical elements of the present invention or delineate the scope ofthe present invention. Its sole purpose is to present some conceptsdisclosed herein in a simplified form as a prelude to the more detaileddescription that is presented later. Many of the attendant features willbe more readily appreciated as the same becomes better understood byreference to the following detailed description considered in connectionwith the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1A and 1B are ¹H NMR (400 MHz, CDCl₃, 298 K) and ¹³C NMR (100 MHz,CDCl₃, 298 K) spectra of CTV1, respectively.

FIGS. 2A and 2B are ¹H NMR (400 MHz, CDCl₃, 298 K) and ¹³C NMR (100 MHz,CDCl₃, 298 K) spectra of CTV2, respectively.

FIGS. 3A and 3B are ¹H NMR (400 MHz, CDCl₃, 298 K) and ¹³C NMR (100 MHz,CDCl₃, 298 K) spectra of CTV3, respectively.

FIGS. 4A and 4B are ¹H NMR (400 MHz, CDCl₃, 298 K) and ¹³C NMR (100 MHz,CDCl₃, 298 K) spectra of CTV4, respectively.

FIGS. 5A and 5B are ¹H NMR (400 MHz, CDCl₃, 298 K) and ¹³C NMR (100 MHz,CDCl₃, 298 K) spectra of CTV5, respectively.

FIGS. 6A and 6B are ¹H NMR (400 MHz, CDCl₃, 298 K) and ¹³C NMR (100 MHz,CDCl₃, 298 K) spectra of CTV6, respectively.

FIGS. 7A and 7B are ¹H NMR and ¹³C NMR spectra of CTV7, respectively.

FIG. 8 is ¹H NMR spectrum of CTV8.

FIG. 9 is ¹H NMR spectrum of CTV9.

FIGS. 10A and 10B are ¹H NMR and ¹³C NMR spectra of CTV10, respectively.

FIGS. 11A and 11B are ¹H NMR and ¹³C NMR spectra of CTV11, respectively.

FIGS. 12A and 12B are ¹H NMR and ¹³C NMR spectra of CTV12, respectively.

FIGS. 13(A), 13(B), 13(C), and 13(D) are ¹H NMR spectrum (400 MHz,CDCl₂CDCl₂, 298 K) of CTV1, an equimolar mixture of C₆₀ and CTV1, anequimolar mixture of C₇₀ and CTV1, and purified C₇₀ CTV1 hemicarceplex,respectively.

FIGS. 14(A), 14(B), 14(C), and 14(D) are ¹³C NMR spectrum (400 MHz,CDCl₂CDCl₂, 298 K) of CTV1, an equimolar mixture of C₆₀ and CTV1,purified C₇₀, and purified C₇₀ CTV1 hemicarceplex, respectively.

FIGS. 15A and 15B are ¹H NMR (400 MHz, CDCl₃, 298 K) and ¹³C NMR (100MHz, CDCl₃, 298 K) spectra of hemicarceplex C₇₀ CTV2, respectively.

FIGS. 16A and 16B are ¹H NMR (400 MHz, CDCl₃, 298 K) and ¹³C NMR (200MHz, CDCl₃, 298 K) spectra of hemicarceplex C₆₀ CTV3, respectively.

FIG. 17 is the ¹H NMR (400 MHz, CDCl₃, 298 K) spectrum of hemicarceplexSc3N@C₈₀ CTV4.

FIGS. 18A and 18B are ¹H NMR (400 MHz, CDCl₃, 298 K) spectra of theequimolar mixture of CTV5 to C₆₀ and C₇₀, respectively.

FIGS. 19(A) and 19(B) are the ¹H NMR (400 MHz, CDCl₃, 298 K) spectra offree CTV6, and the equimolar mixture of CTV6 and C₆₀, respectively.

FIG. 20 is ¹H NMR spectra of the purified C₇₆⊙CTV7 and C₇₈⊙CTV7hemicarceplexes.

FIG. 21 is ¹H NMR of the purified CO₈₄⊙CTV8 hemicarceplex.

FIG. 22 is ¹H NMR spectrum fullerenes⊙CTV9 complexes.

FIG. 23 is ¹H NMR spectrum fullerenes⊙CTV10 complexes.

FIGS. 24A and 24B are ¹H NMR and ¹³C NMR spectra of the purifiedC₆₀⊙CTV11 hemicarceplex, respectively.

FIGS. 25A and 25B are ¹H NMR and ¹³C NMR spectra of the purifiedC₆₀⊙CTV12 hemicarceplex, respectively.

FIG. 26 is HPLC analysis results of the fullerene mixture released fromC₇₆⊙CTV7 and C₇₈®CTV7 hemicarceplexes.

FIG. 27 is HPLC analysis results of the fullerene mixture released fromC₈₄⊙CTV8 hemicarceplexes.

FIG. 28 is a process flow diagram of isolating fullerene⊙CTVhemicarceplexes by column chromatography.

DETAILED DESCRIPTION

In the following detailed description, for purposes of explanation,numerous specific details are set forth in order to provide a thoroughunderstanding of the disclosed embodiments. It will be apparent,however, that one or more embodiments may be practiced without thesespecific details.

Synthesizing Cyclotriveratrylenes (CTVs) For Forming Fullerene CTVHemicarceplexes

Cyclotriveratrylene-based molecular cages (abbreviated as CTVs below)for forming fullerene CTV complexes or hemicarceplexes were synthesizedfirst. The CTV host molecule has a chemical structure shown below,wherein LS1 and LS2 represent first and second linking spacers.

According to an embodiment, at least three of the first and secondlinking spacers are alkyl chains containing at least 10 carbons, such as10-15 carbons. According to another embodiment, at least one of thefirst and second linking spacers containing a diester linkage. Six CTVhost molecules were synthesized, and the first and the second linkingspacers are listed in the table below. Please note that the firstlinking spacers LS1 and the second linking spacers LS2 listed below areexchangeable, since it is the chain length of the first and the secondlinking spacers that are matters about the accommodation of a guestfullerene or a derivative thereof.

CTV host LS1 LS2 CTV1 —(CH₂)₁₂— —(CH₂)₁₂— CTV2 —(CH₂)₁₁— —(CH₂)₁₂— CTV3—(CH₂)₁₀— —(CH₂)₁₂— CTV4 —(CH₂)₁₂—

CTV5 —(CH₂)₁₁—

CTV6 —(CH₂)₁₀—

CTV7 —(CH₂)₁₂— —(CH₂)₁₃— CTV8 —(CH₂)₁₂— —(CH₂)₁₄— CTV9 —(CH₂)₁₂——(CH₂)₁₅— CTV10 —(CH₂)₁₃— —(CH₂)₁₄— CTV11 —(CH₂)₁₀— —(CH₂)₁₀— CTV12—(CH₂)₁₀— —(CH₂)₁₁—

Synthesis of CTV1

Dialdehyde S2: The reaction of 3,4-dihydroxybenzaldehyde (5.17 g, 37.4mmol), 1,12-dibromododecane (5.58 g, 17.0 mmol), and KHCO₃ (3.74 g, 37.4mmol) in DMF (75 mL) at 65° C. for 3 days afforded themonoalkylated-dialdehyde S1, which was dissolved with 1,12-dibromodecane(3.71 g, 11.3 mmol) in DMF (130 mL) and reacted with K₂CO₃ (9.37 g, 67.8mmol) in DMF (1 L) to afford a white solid S2 (2.35 g, 34%).

Mp: 175-176° C.; ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.25-1.39 (m, 24H),1.45-1.55 (m, 8H), 1.75-1.86 (m, 8H), 4.03 (t, J=5.6 Hz, 4H), 4.06 (t,J=5.6 Hz, 4H), 6.92 (d, J=8 Hz, 2H), 7.37 (d, J=2 Hz, 2H), 7.40 (dd,J=8, 2 Hz, 2H), 9.81 (s, 2H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=26.4,26.4, 29.2, 29.3, 29.6, 29.6, 29.8, 29.8, 29.8, 29.8, 69.0, 69.1, 111.2,111.9, 126.6, 129.9, 149.6, 154.9, 191.0; HR-MS (ESI): calcd forC₃₈H₅₆O₆Na⁺ [M+Na]⁺, m/z 631.3975; found, m/z 631.3972.

Diol S3: Following the procedure described above for S2, the reaction ofthe dialdehyde S2 (1.92 g, 3.16 mmol) and NaBH₄ (0.36 g, 9.47 mmol) inisopropyl alcohol (79 mL) and CH₂Cl₂ (79 mL) under reflux for 16 hafforded a white solid S3 (1.89 g, 98%).

Mp: 153-154° C.; ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.18-1.38 (m, 24H),1.43-1.53 (m, 8H), 1.73-1.82 (m, 8H), 3.97 (t, J=6.4 Hz, 4H), 3.98 (t,J=6.4 Hz, 4H), 4.58 (s, 4H), 6.84 (s, 4H), 6.91 (s, 2H); ¹³C NMR (100MHz, CDCl₃, 298 K): δ=26.1, 26.3, 26.4, 29.4, 29.5, 29.5, 29.6, 29.7,29.8, 29.8, 65.4, 69.3, 69.5, 113.2, 114.2, 119.7, 133.8, 149.0, 149.6;HR-MS (ESI): calcd for C₃₈H₆₀O₆Na⁺ [M+Na]⁺, m/z 635.4288; found, m/z635.4285.

Mono-alcohol S4: Following the procedure described above for S3, thereaction of the diol S3 (0.1 g, 0.163 mmol), pyridinium chlorochromate(53 mg, 245 pmole), 4-Å molecular sieves (0.75 g), and Celite (1.49 g)in CH₂Cl₂ (5.2 mL) and DMF (3 mL) at 60° C. for 3 h afforded a whitesolid S4 (39 mg, 37%).

Mp: 166-168° C.; ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.25-1.39 (m, 24H),1.44-1.55 (m, 8H), 1.73-1.86 (m, 8H), 3.93-4.01 (m, 4H), 4.01-4.09 (m,4H), 4.58 (d, J=5.2 Hz, 2H), 6.84 (s, 2H), 6.91-6.93 (m, 2H), 7.36-7.42(m, 2H), 9.81 (s, 1H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=26.4, 29.2,29.3, 29.6, 29.6, 29.7, 29.8, 29.8, 65.4, 69.1, 69.1, 69.3, 69.5 (12signals are missing, possibly because of signal overlapping), 111.2,111.9, 113.2, 114.2, 119.7, 126.6, 129.9, 133.9, 148.9, 149.6, 149.6,154.9, 191.0; HR-MS (ESI): calcd for C₃₈H₅₈O₆Na⁺ [M+Na]⁺, m/z 633.4131;found, m/z 633.4141.

Triol S5: Following the procedure described above for S4, the reactionof the mono-alcohol S4 (1.33 g, 2.18 mmol) and Sc(OTf)₃ (54 mg, 0.11mmol) in CHCl₃ (11 mL) at 70° C. for 16 h afforded the trialdehyde as alight yellow solid, which was reacted with NaBH₄ (50 mg, 1.21 mmole) inisopropyl alcohol (30 mL) and CH₂Cl₂ (30 mL) at room temperature for 16h to afford a white solid S5 (0.25 g, 19%).

Mp: 117-119° C.; ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.20-1.52 (m, 96H),1.67-1.81 (m, 24H), 3.46 (d, J=13.6 Hz, 3H), 3.82-3.89 (m, 6H),3.92-3.99 (m, 18H), 4.56 (s, 6H), 4.68 (d, J=13.6 Hz, 3H), 6.80 (s, 6H),6.83 (s, 6H), 6.89 (s, 3H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=26.3,26.3, 26.4, 29.5, 29.6, 29.6, 29.8, 29.8, 29.8, 36.4, 65.3, 69.2, 69.5,69.7, 113.2, 114.2, 116.2, 119.7, 132.3, 133.9, 148.0, 148.9, 149.6 (12aliphatic and 3 aromatic signals are missing, possibly because of signaloverlapping); HR-MS (ESI): calcd for C₁₁₄H₁₇₄O₁₅ ⁺ [M]⁺, m/z 1783.2853;found, m/z 1783.2791.

CTV1: Following the procedure described above for S5, the reaction ofthe triol S5 (0.10 g, 0.056 mmol) and scandium triflate (60 mg, 0.12mmol) in CHCl₃ (25 mL/30 mL) at 60° C. for 2 days afforded a white solidCTV1 (33 mg, 34%). The ¹H NMR and ¹³C NMR spectra of CTV1 are shown inFIGS. 1A and 1B. All related spectral data are listed below.

Mp: 258° C. (dec); ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.12-1.42 (m, 96H),1.60-1.83 (m, 24H), 3.46 (d, J=13.6 Hz, 6H), 3.77-3.86 (m, 12H),4.00-4.07 (m, 12H), 4.68 (d, J=13.6, 6H), 6.80 (s, 12H); ¹³C NMR (100MHz, CDCl₃, 298 K): δ=26.3, 29.4, 29.8, 30.2, 30.2, 36.4, 69.1, 115.6,132.1, 147.6; HR-MS (ESI): calcd for C₁₁₄H₁₆₈O₁₂Na⁺ [M+Na]⁺, m/z1752.2432; found, m/z 1752.2488.

Synthesis of CTV2

Aldehyde S6: The reaction of potassium bicarbonate (0.67 g, 6.70 mmol),3,4-dihydroxybenzaldehyde (0.93 g, 6.70 mmol), and 1,12-dibromododecane(2.00 g, 6.09 mmol) in DMF (60 mL) at 55° C. for 40 h afforded aldehydeS6 as a white solid (0.81 g, 34%).

Mp: 74-75° C.; ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.20-1.46 (m, 16H),1.75-1.84 (m, 4H), 3.34 (t, J=6.8 Hz, 2H), 4.07 (t, J=6.6 Hz, 2H), 6.04(s, 1H), 6.89 (d, J=8.2 Hz, 1H), 7.35 (dd, J=8.2, 2.0 Hz, 1H), 7.38 (d,J=2 Hz, 1H), 9.77 (s, 1H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.8,28.0, 28.6, 28.8, 29.1, 29.2, 29.3, 32.7, 33.9, 69.2 (2 signals aremissing, possibly because of signal overlapping), 110.8, 113.9, 124.4,130.2, 146.1, 151.3, 190.9; HR-MS (ESI): calcd for C₁₉H₃₀BrO₃ ⁺ [M+H]⁺,m/z 385.1373; found, m/z 385.1380.

Alcohol S7: Following the procedure described above for S6, the reactionof the aldehyde S6 (0.81 g, 2.10 mmol) and NaBH₄ (40 mg, 1.05 mmol) inmethanol (200 mL) at room temperature for 2 h afforded a white solid(0.79 g, 97%). The white solid was then reacted with3,4-dihydroxybenzaldehyde (0.31 g, 2.24 mmol) and potassium bicarbonate(0.23 g, 2.25 mmol) in DMF DMF (50 mL) at 55° C. for 36 h to afford awhite solid S7 (0.58 g, 64%).

Mp: 136-137° C.; ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.25-1.50 (m, 16H),1.73-1.89 (m, 4H), 4.01 (t, J=6.4 Hz, 2H), 4.11 (t, J=6.7 Hz, 2H), 4.56(s, 2H), 5.67 (br, 2H), 6.80 (s, 2H), 6.90-6.96 (m, 2H), 7.36-7.44 (m,2H), 9.81 (s, 1H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.9, 26.0, 29.0,29.2, 29.2, 29.3, 29.5, 29.5, 65.1, 69.1, 69.3 (2 signals are missing,possibly because of signal overlapping), 110.9, 111.6, 113.5, 114.1,118.8, 124.4, 130.5, 134.2, 145.5, 145.9, 146.2, 151.3, 191.0; HR-MS(ESI): calcd for C₂₆H₃₅O₆ ⁻ [M−H]⁻, m/z 443.2439; found, m/z 443.2445.

Macrocycle S8: Following the procedure described above for S7, thereaction of the diol S7 (3.74 g, 8.4 mmol), 1,11-dibromoundecane (2.6 4g, 8.4 mmol) and K₂CO₃ (13.9 g, 101 mmol) in DMF (840 mL) at 60° C. for5 days afforded a white solid S8 (2.01 g, 40%).

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.25-1.40 (m, 22H), 1.44-1.57 (m, 8H),1.74-1.87 (m, 8H), 3.94-3.99 (m, 4H), 4.00-4.09 (m, 4H), 4.58 (s, 2H),6.83 (s, 2H), 6.88-6.94 (m, 2H), 7.34-7.41 (m, 2H), 9.78 (s, 1H); ¹³CNMR (100 MHz, CDCl₃, 298 K): ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=26.4,26.4, 26.5, 26.6, 29.3, 29.4, 29.6, 29.6, 29.6, 29.7, 29.7, 29.8, 29.8,29.8, 29.9, 30.0, 30.1, 65.3, 69.0, 69.1, 69.4, (3 signals missing,possibly because of signal overlap), 111.8, 111.6, 112.8, 113.9, 119.4,126.5, 129.7, 133.7, 148.6, 149.3, 149.3, 154.6, 190.7; HR-MS (ESI):calcd for C₃₇H₅₆O₆Na⁺ [M+Na]⁺, m/z 619.40; found, m/z 619.39746.

Trialdehyde S9: Following the procedure described above for S8, thereaction of the macrocycle S8 (0.2 g, 0.34 mmol) and Sc(OTf)₃ (8.4 mg,0.017 mmol) in CHCl₃ (3.35 mL) at 70° C. for 16 h afforded alight-yellow solid S9 (55 mg, 29%).

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.20-1.55 (m, 90H), 1.68-1.87 (m,24H), 3.46 (d, J=14.0 Hz, 3H), 3.82-4.10 (m, 24H), 4.68 (d, J=14.0 Hz,3H), 6.80-6.83 (m, 6H), 6.89-6.94 (m, 3H), 7.34-7.41 (m, 6H), 9.79 (s,3H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=29.2, 29.3, 29.5, 29.6, 29.7,29.7, 29.7, 29.9, 29.9, 29.9, 36.5, 69.1, 69.1, 69.5, 69.7 (9 signalsare missing, possibly because of signal overlapping), 111.0, 111.8,116.0, 116.3, 126.6, 129.9, 132.2, 132.3, 147.9, 148.0, 149.6, 154.8,191.0; HR-MS (ESI): calcd for C₁₁₁H₁₆₂O₁₅Na⁺ [M+Na]⁺, m/z 1758.1811;found, m/z 1758.1812.

CTV2: Following the procedure described above for S9, the reaction ofthe trialdehyde S9 (55 mg, 32 μmol) and NaBH₄ (4.84 mg, 0.13 mmol) inisopropyl alcohol (1 mL) and CH₂Cl₂ (1 mL) at room temperature for 16 hafford a white solid. The white solid was ten reacted with scandiumtriflate (11 mg, 23 μmol) in CHCl₃ (10 mL) at 60° C. for 3 days toafford a white solid CTV2 (15 mg, 28%). The ¹H NMR and ¹³C NMR spectraof CTV2 are shown in FIGS. 2A and 2B. All related spectral data arelisted below.

Mp: >261° C. (dec.); ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.11-1.46 (m,90H), 1.57-1.85 (m, 24H), 3.45 (d, J=13.8 Hz, 6H), 3.71-3.88 (m, 12H),4.00-4.10 (m, 12H), 4.68 (d, J=13.7, 6H), 6.77 (s, 6H), 6.79 (s, 6H);¹³C NMR (100 MHz, CDCl₃, 298 K): δ=26.0, 27.3, 29.2, 29.3, 29.6, 29.7,30.1, 30.3, 30.8, 36.3, 68.5, 69.5, 114.9, 131.9, 147.4, 147.8 (3signals missing, possibly because of signal overlap); HR-MS (ESI): calcdfor C₁₁₁H₁₆₂O₁₂Na⁺ [M+Na]⁺, m/z 1710.20; found, m/z 1710.19641.

Synthesis of CTV3

Macrocycle S10: Following the procedure described above for S7, thereaction of the diol S7 (3.74 g, 8.4 mmol), 1,10-dibromodecane (2.52 g,8.4 mmol) and K₂CO₃ (13.9 g, 101 mmol) in DMF (840 mL) at 60° C. for 5days afforded a white solid S10 (1.88 g, 77%).

Macrocycle S10: ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.26-1.40 (m, 20H),1.45-1.53 (m, 8H), 1.73-1.86 (m, 8H), 3.95-4.00 (m, 4H), 4.01-4.09 (m,4H), 4.58 (s, 2H), 6.83 (s, 2H), 6.89-6.94 (m, 2H), 7.36-7.41 (m, 2H),9.80 (s, 1H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=26.2, 26.3, 26.5, 26.5,29.2, 29.4, 29.5, 29.6, 29.7, 29.7, 29.8, 29.9, 29.9, 65.4, 69.0, 69.1,69.5, (7 signals missing, possibly because of signal overlap) 111.1,111.8, 113.0, 114.2, 119.6, 126.6, 129.9, 133.8, 148.9, 149.6, 154.9,191.0 (1 signals missing, possibly because of signal overlap); HR-MS(ESI): calcd for C₃₆H₅₄O₆ ⁺ [M]⁺, m/z 582.3920; found, m/z 582.3901.

Trialdehyde S11: Following the procedure described above for S10, thereaction of the macrocycle S10 (1.88 g, 3.23 mmol) and Sc(OTf)₃ (79.6mg, 0.16 mmol) in CHCl₃ (18.8 mL) at 70° C. for 16 h afforded alight-yellow solid S11 (215.2 mg, 12%).

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.20-1.56 (m, 88H), 1.68-1.88 (m,24H), 3.47 (d, J=13.8 3H), 3.84-4.10 (m, 24H), 4.68 (d, J=13.6 Hz, 3H),6.79-6.82 (m, 6H), 6.89-6.94 (m, 3H), 7.35-7.41 (m, 6H), 9.79 (s, 3H);¹³C NMR (100 MHz, CDCl₃, 298 K): δ=26.2, 26.3, 26.4, 26.5, 29.2, 29.2,29.4, 29.5, 29.5, 29.6, 29.6, 29.7, 29.8, 29.9, 36.4, 69.0, 69.1, 69.5,69.7, (4 signals are missing, possibly because of signal overlapping),111.0, 111.8, 116.0, 116.3, 126.6, 129.9, 132.2, 132.3, 147.9, 148.0,149.6, 154.8, 191.0; HR-MS (ESI): calcd for C₁₀₈H₁₅₆O₁₅ ⁺ [M]⁺, m/z1693.1444; found, m/z 1693.1444.

CTV3: Following the procedure described above for S11, the reaction ofthe trialdehyde S11 (215 mg, 130 ┌mol) and NaBH₄ (19.2 mg, 0.51 mmol) inisopropyl alcohol (5.5 mL) and CH₂Cl₂ (5.5 mL) at room temperature for16 h afford a white solid. The white solid was ten reacted with scandiumtriflate (81.4 mg, 165 ┌mol) in CHCl₃ (94 mL) at 60° C. for 3 days toafford a white solid CTV3 (30 mg, 14%). The ¹H NMR and ¹³C NMR spectraof CTV3 are shown in FIGS. 3A and 3B. All related spectral data arelisted below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.12-1.44 (m, 84H), 1.57-1.87 (m,24H), 3.45 (d, J=13.6 Hz, 6H), 3.77-3.90 (m, 12H), 3.96-4.06 (m, 12H),4.67 (d, J=13.6, 6H), 6.77 (s, 6H), 6.83 (s, 6H); ¹³C NMR (100 MHz,CDCl₃, 298 K): δ=25.9, 26.3, 29.0, 29.2, 29.9, 30.2, 30.5, 31.6, 36.4,68.0, 70.7, (1 signals are missing, possibly because of signaloverlapping), 114.3, 117.6, 131.6, 132.9, 147.2, 148.3; HR-MS (ESI):calcd for C₁₀₈H₁₅₆O₁₂ [M]⁺, m/z 1645.1597; found, m/z 1645.1632.

Synthesis of CTV4

Macrocycle S12: Following the procedure described above for S7, thereaction of the diol S7 (2.00 g, 4.50 mmol), bis(4-bromobutyl) succinate(1.75 g, 4.50 mmol) and K₂CO₃ (3.73 g, 26.99 mmol) in DMF (400 mL) at60° C. for 6 days afforded a white solid S12 (0.59 g, 19%).

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.21-1.41 (m, 12H), 1.42-1.55 (m, 4H),1.56-2.00 (m, 12H), 2.60 (s, 4H), 3.40-4.06 (m, 8H), 4.18-4.21 (m, 4H),4.58 (s, 2H), 6.81-6.93 (m, 4H), 7.35 (d, J=1.6 Hz, 1H), 7.40 (dd,J=8.4, 1.8 Hz, 1H), 9.79 (s, 1H); ¹³C NMR (100 MHz, CDCl₃, 298 K):δ=26.2, 26.3, 29.2, 29.2, 29.4, 29.5, 29.5, 29.6, 29.6, 64.6, 64.7,65.3, 68.7, 68.7, 69.0, 69.2, 110.9, 111.5, 113.1, 113.5, 119.8, 126.8,129.6, 133.5, 148.7, 148.8, 149.0, 154.6, 171.9, 172.0, 190.7 (sevenaliphatic signals are missing, possibly because of signal overlapping);HR-MS (ESI): calcd for C₃₈H₅₄O₁₀Na⁺ [M+Na]⁺, m/z 693.3615; found, m/z693.3625.

Trialdehyde S13: Following the procedure described above for S12, thereaction of the mono-alcohol S12 (1.82 g, 2.71 mmol) and Sc(OTf)₃ (67mg, 0.140 mmol) in CHCl₃ (14 mL) at 70° C. for 16 h afforded thetrialdehyde as a light-yellow oil S13 (274 mg, 15%).

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.16-1.52 (m, 42H), 1.67-1.94 (m,42H), 2.56 (s, 12H), 3.46 (d, J=13.6 Hz, 3H), 3.78-4.00 (m, 12H),4.00-4.09 (m, 12H), 4.09-4.24 (m, 12H), 4.67 (d, J=13.6, 3H), 6.79 (s,3H), 6.80 (s, 3H), 6.91 (d, J=8.0 Hz, 3H), 7.35 (d, J=1.6 Hz, 3H), 7.39(dd, J=8.2, 1.8 Hz, 3H), 9.79 (s, 3H); ¹³C NMR (100 MHz, CDCl₃, 298 K):δ=25.6, 25.7, 26.0, 26.1, 29.0, 29.2, 29.3, 29.3, 29.4, 29.4, 29.5,36.3, 64.5, 68.5, 68.9, 69.2, 69.3, 110.8, 111.5, 115.6, 116.4, 126.9,130.0, 132.0, 132.5, 147.5, 148.0, 149.1, 154.7, 172.1, 190.8 (sixaliphatic and one aromatic signals are missing, possibly because ofsignal overlapping); HR-MS (ESI): calcd for C₁₁₄H₁₅₆O₂₇Na⁺ [M+Na]⁺, m/z1980.0732; found, m/z 1980.0764.

CTV4: Following the procedure described above for S13, the reaction ofthe trialdehyde S13 (274 mg, 0.14 mmol) and NaBH₄ (16 mg, 0.42 mmol) inmethanol (4.7 mL) and CH₂Cl₂ (9.3 mL) at −15° C. for 3.5 h afford awhite solid. The white solid was then reacted with 10% TFA (15 mL) inCHCl₃ (102 mL) at room temperature for 2 days to afford a white solidCTV4 (16 mg, 6%). The ¹H NMR and ¹³C NMR spectra of CTV4 are shown inFIGS. 4A and 4B. All related spectral data are listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.13-1.45 (m, 42H), 1.59-1.89 (m,42H), 2.56 (s, 12H), 3.45 (d, J=13.6 Hz, 6H), 3.75-3.91 (m, 12H),3.91-4.05 (m, 12H), 4.06-4.21 (br, 12H), 4.67 (d, J=14.0, 6H), 6.78 (s,6H), 6.79 (s, 6H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.7, 26.1, 26.1,29.2, 29.5, 29.7, 29.7, 29.8, 36.4, 64.4, 69.0, 69.4, 115.9, 116.1,132.2, 132.5, 147.7, 147.9, 172.0; HR-MS (ESI): calcd for C₁₁₄H₁₅₆NaO₂₄⁺ [M+Na]⁺, m/z 1932.0884; found, m/z 1931.9346.

Synthesis of CTV5

Aldehyde S14: The reaction of potassium bicarbonate (7.16 g, 70.8 mmol),3,4-dihydroxybenzaldehyde (8.15 g, 59.0 mmol), and 1,11-dibromoundecane(22.3 g, 70.8 mmol) in DMF (393 mL) at 60° C. for 2 days affordedaldehyde S14 as a white solid (6.38 g, 29%).

Mp: 60-61° C.; ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.28-1.48 (m, 14H),1.79-1.87 (m, 4H), 3.38 (t, J=6.8 Hz, 2H), 4.11 (t, J=6.4 Hz, 2H), 5.75(s, 1H), 6.93 (d, J=8.4 Hz, 1H), 7.39 (dd, J=8.4, 2 Hz, 1H), 7.42 (d,J=2 Hz, 1H), 9.81 (s, 1H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.9,28.1, 28.7, 29.0, 29.2, 29.3, 29.4, 29.4, 32.8, 34.0, 69.3, 110.9,114.0, 124.4, 130.5, 146.2, 151.2, 190.9; HR-MS (ESI): calcd forC₁₈H₂₆O₃Br⁻ [M−H]⁻, m/z 369.1065; found, m/z 369.1062.

Alcohol S15: Following the procedure described above for S14, thereaction of the aldehyde S14 (6.38 g, 17.19 mmol) and NaBH₄ (650 mg,17.19 mmol) in methanol (30 mL) and CH₂Cl₂ (60 mL) at room temperaturefor 2 h afforded a white solid (1.89 g, 98%). The white solid was thenreacted with 3,4-dihydroxybenzaldehyde (2.62 g, 18.94 mmol) andpotassium bicarbonate (1.92 g, 18.94 mmol) in DMF (115 mL) at 60° C. for2 days to afford a white solid S15 (4.19 g, 57%).

Mp: 94-97° C.; ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.29-1.48 (m, 14H),1.75-1.87 (m, 4H), 4.01 (t, J=6.4 Hz, 2H), 4.11 (t, J=6.8 Hz, 2H), 4.56(s, 2H), 5.68 (s, 1H), 5.81 (s, 1H), 6.78-6.82 (m, 2H), 6.91-6.93 (m,2H), 7.38 (dd, J=8, 2 Hz, 1H), 7.41 (d, J=2 Hz, 1H), 9.81 (s, 1H); ¹³CNMR (100 MHz, CDCl₃, 298 K): δ=25.9, 25.9, 29.0, 29.2, 29.2, 29.3, 29.4,29.4, 29.4, 65.1, 69.0, 69.3, 110.9, 111.6, 113.5, 114.1, 118.8, 124.4,130.5, 134.2, 145.5, 145.9, 146.2, 151.3, 191.0; HR-MS (ESI): calcd forC₂₅H₃₃O₆ ⁻ [M−H]⁻, m/z 429.2277; found, m/z 429.2272.

Macrocycle S16: Following the procedure described above for S15, thereaction of the diol S15 (3.64 g, 8.46 mmol), Bis(4-bromobutyl)succinate (3.28 g, 8.46 mmol) and K₂CO₃ (7.02 g, 50.77 mmol) in DMF (846mL) at 60° C. for 5 days afforded a white solid S16 (1.83 g, 34%).

Mp: 125-127° C.; ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.29-1.33 (m, 10H),1.42-1.49 (m, 4H), 1.70-1.89 (m, 12H), 2.59 (s, 4H), 3.93-4.05 (m, 8H),4.17-4.20 (m, 4H), 4.56 (s, 2H), 6.80-6.93 (m, 4H), 7.35 (d, J=1.6 Hz,1H), 7.40 (dd, J=8.4, 1.6 Hz, 1H), 9.79 (s, 1H); ¹³C NMR (100 MHz,CDCl₃, 298 K): δ=25.6, 25.7, 25.8, 25.9, 26.2, 26.2, 29.1, 29.2, 29.4,29.4, 29.5, 29.6, 29.6, 64.5, 64.6, 65.2, 68.6, 68.7, 69.0, 69.2, 111.0,111.6, 113.2, 113.6, 119.9, 126.9, 129.8, 133.7, 148.8, 149.0, 149.2,154.8, 172.1, 172.1, 190.9; HR-MS (ESI): calcd for C₃₇H₅₂O₁₀Na⁺ [M+Na]⁺,m/z 679.3458; found, m/z 679.3466.

Trialdehyde S17: Following the procedure described above for S16, thereaction of the macrocycle S16 (700 mg, 1.07 mmol) and Sc(OTf)₃ (26 mg,0.053 mmol) in CHCl₃ (14 mL) at room temperature for 16 h afforded alight-yellow oil (180 mg, 26%).

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.32-1.48 (m, 36H), 1.69-1.86 (m,42H), 2.56 (s, 12H), 3.45 (d, J=14 Hz, 3H), 3.83-4.05 (m, 24H),4.14-4.19 (m, 12H), 4.67 (d, J=13.6 Hz, 3H), 6.79 (s, 3H), 6.79 (s, 3H),6.91 (d, J=8.4 Hz, 3H), 7.35 (d, J=1.6 Hz, 3H), 7.39 (dd, J=8.4, 1.6 Hz,3H), 9.79 (s, 3H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.6, 25.6, 25.7,26.0, 26.1, 26.2, 29.0, 29.4, 29.4, 29.4, 29.5, 29.6, 36.3, 64.4, 68.6,69.0, 69.2, 69.4, 111.0, 111.6, 115.8, 116.5, 126.8, 129.8, 132.1,132.6, 147.6, 148.0, 149.1, 154.7, 172.0, 190.7 (four aliphatic and onearomatic signals are missing, possibly because of signal overlapping);HR-MS (ESI): calcd for C₁₁₁H₁₅₀O₂₇Na⁺ [M+Na]⁺, m/z 1938.0261; found, m/z1938.0191.

CTV5: Following the procedure described above for S17, the reaction ofthe trialdehyde S17 (100 mg, 0.052 mmol) and NaBH₄ (4 mg, 0.1 mmol) inmethanol (1.7 mL) and CH₂Cl₂ (3.4 mL) at −15° C. for 1.5 h afford awhite solid. The white solid was then reacted with TFA (8 mL) in CHCl₃(57 mL) at room temperature for 2 days to afford a white solid CTV5 (12mg, 12%). The ¹H NMR and ¹³C NMR spectra of CTV5 are shown in FIGS. 5Aand 5B. All related spectral data are listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.20-1.38 (m, 36H), 1.55-1.78 (m,42H), 2.56 (s, 12H), 3.45 (d, J=13.6 Hz, 6H), 3.75-3.85 (m, 12H),3.93-4.03 (m, 12H), 4.14 (br, 12H), 4.67 (d, J=13.6, 6H), 6.75 (s, 6H),6.79 (s, 6H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.7, 26.1, 26.7, 29.3,29.4, 29.6, 30.0 (one signal missing, possibly because of signaloverlap), 36.3, 64.4, 69.1, 69.3, 114.8, 116.3, 131.8, 132.6, 147.3,148.1, 172.0; HR-MS (ESI): calcd for C₁₁₁H₁₅₀NaO₂₄+[M+Na]⁺, m/z1890.0414; found, m/z 1890.0342.

Synthesis of CTV6

Macrocycle S18: The reaction of the potassium bicarbonate (1.22 g, 12.03mmol), 3,4-dihydroxybenzaldehyde (1.66 g, 12.03 mmol), and1,10-dibromodecane (1.64 g, 5.47 mmol) in DMF (11 mL) at 65° C. for 2days afforded a white solid. The white solid was then reacted with(bis(4-bromobutyl) succinate) (1.66 g, 4.28 mmol) and K₂CO₃ in DMF (427mL) to afford a white solid S18 (3.64 g, 40%).

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.33-1.50 (m, 12H), 1.79-1.87 (m,12H), 2.59 (s, 4H), 4.02-4.05 (m, 8H), 4.18-4.21 (m, 4H), 6.92 (d, J=8.4Hz, 2H), 7.35 (d, J=1.6 Hz, 2H), 7.40 (dd, J=8, 1.2 Hz, 2H), 9.80 (s,2H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.6, 25.9, 26.2, 29.1, 29.1,29.4, 29.5, 64.6, 68.7, 69.0, 110.9, 111.6, 126.9, 129.8, 149.2, 154.7,172.1, 190.9; HR-MS (ESI): calcd for C₃₆H₄₈O₁₀Na⁺ [M+Na]⁺, m/z 663.3145;found, m/z 663.3177.

Alcohol S19: Following the procedure described above for S18, thereaction of the dialdehyde S18 (2.13 g, 3.33 mmol) and NaBH₄ (126 mg,3.33 mmol) in methanol (50 mL) and CH₂Cl₂ (50 mL) at 0° C. for 2 hafforded a white solid. The following reaction of the white solid,pyridinium chlorochromate (669 mg, 3.10 mmol) and 4-Å molecular sieves(2 g) in CH₂Cl₂ (124 mL) at room temperature for 3 h afforded a whitesolid S19 (712 mg, 22%).

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.32 (br, 8H), 1.43-1.48 (m, 4H),1.74-1.89 (m, 12H), 2.59 (s, 4H), 3.93-4.07 (m, 8H), 4.19-4.21 (m, 4H),4.57 (s, 2H), 6.80-6.93 (m, 4H), 7.35 (d, J=1.6 Hz, 1H), 7.40 (dd, J=8,1.6 Hz, 1H), 9.80 (s, 1H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.6,25.8, 25.9, 25.9, 26.1, 26.2, 29.0, 29.2, 29.3, 29.4, 29.5, 29.5, (twosignals missing, possibly because of signal overlap), 64.6, 64.6, 65.2,68.7, 68.7, 69.0, 69.2, 110.9, 111.6, 113.1, 113.5, 119.9, 126.9, 129.8,133.7, 148.8, 149.0, 149.2, 154.8, 172.1, (one signal missing, possiblybecause of signal overlap), 190.9; HR-MS (ESI): calcd for C₃₆H₅₀O₁₀Na⁺[M+Na]⁺, m/z 665.3302; found, m/z 665.3344.

Trialdehyde S20: Following the procedure described above for S19, thereaction of the mono-alcohol S19 (500 mg, 0.78 mmol) and Sc(OTf)₃ (19mg, 0.039 mmol) in CHCl₃ (8 mL) at 70° C. for 16 h afforded thetrialdehyde as a light-yellow oil S20 (118 mg, 24%).

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.30-1.47 (m, 30H), 1.69-1.85 (m,42H), 2.55 (s, 12H), 3.45 (d, J=13.6 Hz, 3H), 3.82-4.04 (m, 24H),4.14-4.20 (m, 12H), 4.67 (d, J=13.6 Hz, 3H), 6.78 (s, 3H), 6.79 (s, 3H),6.91 (d, J=8.4 Hz, 3H), 7.34 (s, 3H), 7.39 (d, J=8.4, 3H), 9.79 (s, 3H);¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.5, 25.7, 25.8, 25.9, 26.1, 26.2,29.0, 29.0, 29.3, 29.3, 29.4, 29.4, 29.5, 36.3, 64.5, 64.5, 68.6, 68.9,69.2, 69.3, 110.8, 111.5, 115.6, 116.4, 126.8, 129.7, 132.0, 132.5,147.5, 148.0, 149.1, 154.7, 172.0, 172.0, 190.8 (one aliphatic signal ismissing, possibly because of signal overlap); HR-MS (ESI): calcd forC₁₀₈H₁₄₄O₂₇Na⁺ [M+Na]⁺, m/z 1895.9793; found, m/z 1895.9826.

CTV6: Following the procedure described above for S20, the reaction ofthe trialdehyde S20 (58 mg, 0.031 mmol) and NaBH₄ (4 mg, 0.047 mmol) inmethanol (1.5 mL) and CH₂Cl₂ (1.5 mL) at 0° C. for 1.5 h afford a whitesolid. The white solid was then reacted with TFA (3 mL) in CHCl₃ (50 mL)at room temperature for 2 days to afford a white solid CTV6 (8 mg, 14%).The ¹H NMR and ¹³C NMR spectra of CTV6 are shown in FIGS. 6A and 6B, Allrelated spectral data are listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.23-1.39 (m, 30H), 1.64-1.82 (m,42H), 2.58 (s, 12H), 3.45 (d, J=13.6 Hz, 6H), 3.79-3.87 (m, 12H),3.91-4.00 (m, 12H), 4.15-4.16 (br, 12H), 4.66 (d, J=13.2 Hz, 6H), 6.77(s, 6H), 6.78 (s, 6H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=25.8, 26.1,26.3, 29.5, 29.6, 29.7, 29.8, 36.5, 64.4, 69.1, 69.6, 116.0, 116.3,132.2, 132.4, 147.6, (one signal missing, possibly because of signaloverlap), 171.7; HR-MS (ESI): calcd for C₁₀₈H₁₄₄NaO₂₄ ⁺ [M+Na]⁺, m/z1847.9945; found, m/z 1848.0018.

Synthesis of CTV7

Following similar synthetic procedure described above for CTV2, a CHCl₃(30 mL) solution of the corresponding triol (273 mg, 0.149 mmol) wasadded into a CHCl₃/CH₃NO₂ solution mixture (9/1; 200 mL) of TFA (18 mL)and stirred at room temperature for 60 h to afford CTV7 (43 mg, 16%).The ¹H NMR and ¹³C NMR spectra of CTV7 are shown in FIGS. 7A and 7B,respectively. All related spectral data are listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.14-1.45 (m, 102H), 1.60-1.84 (m,24H), 3.45 (d, J=13.8 Hz, 6H), 3.76-3.90 (m, 12H), 3.98-4.10 (m, 12H),4.67 (d, J=13.6 Hz, 6H), 6.76 (s, 6H), 6.82 (s, 6H); ¹³C NMR (100 MHz,CDCl₃, 298 K): δ=26.4, 26.5, 29.1, 29.5, 29.7, 29.9, 30.1, 30.5, 30.5,36.4, 68.2, 70.0 (one carbon signal was missing possibly because ofsignal overlap), 113.8, 116.5, 131.4, 132.5, 147.1, 148.1. HR-MS (ESI):calcd for C₁₁₇H₁₇₄O₁₂ ⁺ [M]⁺, m/z 1771.3005, found, m/z 1771.3946.

Synthesis of CTV8

Following similar synthetic procedure described above for CTV2, thereaction of the corresponding trialdehyde (157 mg, 843 μmol) and NaBH₄(10 mg, 264 μmol) in isopropyl alcohol (5 mL) and CH₂Cl₂ (10 mL) at roomtemperature for 16 h afford a white solid. The white solid was thenreacted with scandium triflate (44 mg, 894 μmol) in CHCl₃ (30 mL) at 60°C. for 3 days to afford CTV8 (22 mg, 14%). The ¹H NMR spectrum of CTV8is shown in FIG. 8. All related spectral data are listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.14-1.47 (m, 108H), 1.60-1.93 (m,24H), 3.46 (d, J=14.0 Hz, 6H), 3.76-3.90 (m, 12H), 3.96-4.08 (m, 12H),4.68 (d, J=13.6, 6H), 6.77 (s, 6H), 6.82 (s, 6H); HR-MS (ESI): calcd forC₁₂₀H₁₈₀O₁₂ [M], m/z 1813.3475; found, m/z 1813.3495.

Synthesis of CTV9

Following similar synthetic procedure described above for CTV2, thereaction of the corresponding trialdehyde trialdehyde (624 mg, 328 mol)and NaBH₄ (37 mg, 978 μmol) in isopropyl alcohol (10 mL) and CH₂Cl₂ (30mL) at room temperature for 16 h afford a white solid. The white solidwas then reacted with scandium triflate (176 mg, 358 μmol) in CHCl₃ (119mL) at 60° C. for 3 days to afford CTV9 (27 mg, 4%). The ¹H NMR spectrumof CTV9 is shown in FIG. 9. All related spectral data are listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.15-1.47 (m, 114H), 1.60-1.86 (m,24H), 3.46 (d, J=13.6 Hz, 6H), 3.77-3.92 (m, 12H), 3.95-4.07 (m, 12H),4.68 (d, J=13.6, 6H), 6.77 (s, 6H), 6.82 (s, 6H); HR-MS (ESI): calcd forC₁₂₃H₁₈₆O₁₂ [M]⁺, m/z 1855.3944; found, m/z 1855.3911.

Synthesis of CTV10

Following similar synthetic procedure described above for CTV2, thereaction of the corresponding trialdehyde (498 mg, 261 μmol) and NaBH₄(30 mg, 0.793 mmol) in isopropyl alcohol (10 mL) and CH₂Cl₂ (20 mL) atroom temperature for 16 h afforded a white solid. The white solid wasthen reacted with scandium triflate (86 mg, 175 μmol) in CHCl₃ (59 mL)at 60° C. for 3 days to afford CTV10 (15 mg, 3%). The ¹H NMR and ¹³C NMRspectra of CTV10 are shown in FIGS. 10A and 10B, respectively. Allrelated spectral data are listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.12-1.45 (m, 114H), 1.57-1.84 (m,24H), 3.44 (d, J=13.6 Hz, 6H), 3.76-3.87 (m, 12H), 3.99-4.10 (m, 12H),4.69 (d, J=13.6, 6H), 6.77 (s, 6H), 6.78 (s, 6H); ¹³C NMR (100 MHz,CDCl₃, 298 K): δ=26.1, 26.9, 29.2, 29.3, 29.6, 29.7, 29.9, 30.2, 30.6,36.4, 68.6, 69.4, 114.8, 115.1, 132.0, 147.4, 147.6 (four signals weremissing, possibly because of signal overlapping); HR-MS (ESI): calcd forC₁₂₀H₁₈₀O₁₂ [M]⁺, m/z 1855.3944; found, m/z 1855.3902.

Synthesis of CTV11

Following similar synthetic procedure described above for CTV1, thereaction of the corresponding triol (0.49 g, 0.3 mmol) and scandiumtriflate (0.3 g, 0.6 mmol) in CHCl₃ (250 mL) at 60° C. for 2 days toafford CTV11 (0.14 g, 30%). The ¹H NMR and ¹³C NMR spectra of CTV11 areshown in FIGS. 11A and 11B, respectively. All related spectral data arelisted below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.11-1.41 (m, 72H), 1.58-1.81 (m,24H), 3.43 (d, J=13.8 Hz, 6H), 3.78-3.86 (m, 12H), 4.00-4.07 (m, 12H),4.65 (d, J=13.8, 6H), 6.78 (s, 12H); ¹³C NMR (100 MHz, CDCl₃, 298 K):δ=26.1, 29.3, 29.6, 30.0, 36.3, 69.0, 115.8, 132.3, 147.4; HR-MS (ESI):calcd for C₁₀₂H₁₄₄O₁₂Na⁺ [M+Na]⁺, m/z 1584.0555; found, m/z 1584.0594.

Synthesis of CTV12

Following similar synthetic procedure described above for CTV2, thereaction of the corresponding triol (1.0608 g, 0.640 mmol) in CHCl₃ (50mL) and TFA (64 mL) in CHCl₃/CH₃NO₂=4:1 (512/128 mL) was stirred at roomtemperature for 2 days to afford CTV12 (0.41 g, 40%). The ¹H NMR and ¹³CNMR spectra of CTV12 are shown in FIGS. 12A and 12B, respectively. Allrelated spectral data are listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.11-1.48 (m, 78H), 1.57-1.86 (m,24H), 3.44 (d, J=13.6 Hz, 6H), 3.76-3.86 (m, 12H), 3.98-4.10 (m, 12H),4.67 (d, J=13.6, 6H), 6.75 (s, 6H), 6.82 (s, 6H); ¹³C NMR (100 MHz,CDCl₃, 298 K): δ=26.4, 26.6, 29.0, 29.0, 29.3, 29.7, 29.9, 30.1, 30.5,36.3, 68.0, 70.2, 113.4, 116.8, 131.3, 132.7, 146.8, 148.1; HR-MS (ESI):calcd for C₁₀₅H₁₅₀O₁₂ ⁺ [M]⁺, m/z 1603.1127; found, m/z 1603.1162.

Synthesis of Fullerene CTV Complexes

Fullerene CTV complexes, comprising fullerene⊙CTV hemicarceplexes,formed by various cyclotriveratrylene-based molecular cages, and variousfullerene guests or derivatives thereof are disclosed below. Generally,fullerene⊙CTV complexes are formed by mixing a fullerene or a fullerenemixture with a CTV host in a less-polar solvent being capable ofdissolving fullerene CTV complexes at or above room temperature, such as25-80° C.

The meaning of “a complex” above is a supramolecular host-guestassembly, in which the fullerene guest is located inside the cavity ofthe CTV host. The meaning of “a hemicarceplex” above is a roomtemperature-isolatable complex. The meaning of “room temperature” iswithout heating at all. The meaning of “a fullerene” comprises anunmodified fullerene and a derivative thereof. The meaning of “afullerene's derivative” comprises a fullerene molecule trapping an atom,an ion, a molecule or a metal cluster therein, such as Sc₃N@C₈₀.

Generally, the size of the inner space of the CTV host is stronglyrelated to its shortest linking spacer(s). The size of the CTV host'sopenings may be adjusted by changing the length of its longer linkingspacer(s). Thus, the selectivity of fullerene for entering the CTV hostand its entering easiness may be controlled by adjusting the lengths ofboth linking spacers.

Formation of C₆₀ CTV1 Complex

C₆₀ CTV1 complex was synthesized by mixing equimolar of the CTV1 andpurified C₆₀ in CDCl₂CDCl₂.

The ¹H NMR and ¹³C NMR spectra of the equimolar mixture of C₆₀ and CTV1are respectively shown in FIGS. 13B and 14B. In FIG. 13B, thedescriptors (c) and (uc) respectively refer to the complexed anduncomplexed states of the corresponding components. For comparison, the¹H NMR and ¹³C NMR spectra of CTV1 are also respectively shown in FIGS.13A and 14A.

In FIG. 13B, the ¹H NMR spectrum of the 3 mM equimolar mixture of C₆₀and CTV1 shows a new set of signals corresponding to the C₆₀ CTV1complex. Therefore, C₆₀ CTV1 complex was not sufficiently stable forisolation through column chromatography at ambient temperature, and thuscannot be called as hemicarceplex. However, the ¹H NMR spectrum of theequimolar mixture of C₆₀ and CTV1 suggests that the rates for C₆₀ guestentry into and exit from the internal cavity of CTV1 were slow on thetimescale of ¹H NMR spectroscopy at 400 MHz.

In FIG. 14B, the ¹³C NMR spectra of the 2.5 mM equimolar mixture of C₆₀and CTV1 shows an upfield shifting of the signals of C₆₀ within C₆₀ CTV1complex. This implied that the spherical fullerene could also bepositioned favorably within the cavity of CTV1.

Synthesis of C₇₀ CTV1 Hemicarceplex

C₇₀ CTV1 hemicarceplex was synthesized by the following steps. First,equimolar of the CTV1 and C₇₀ were mixed in CDCl₂CDCl₂. Then, themixture was heated at 60° C. for 48 hours to form C₇₀ CTV1hemicarceplex. The ¹H NMR spectrum of the 3 mM equimolar mixture of C₇₀and CTV1 is shown in FIG. 13C.

Another solution of the CTV1 (40 mg, 23 μmol) and C₇₀ (19.4 mg, 23 μmol)in CHCl₂CHCl₂ (5 mL) was stirred at 60° C. for 24 hours and then thesolvent was evaporated under reduced pressure. The residue was purifiedchromatographically (SiO₂; CS₂ then CH₂Cl₂/hexanes, 1:1 in volume ratio)to afford a black solid of C₇₀ CTV1 hemicarceplex (32 mg, 54%).

All related spectral data of the purified C₇₀ CTV1 hemicarceplex areprovided below. Mp: >300° C.; ¹H NMR (400 MHz, CDCl₂CDCl₂, 298 K):δ=1.12-1.57 (m, 96H), 1.68-1.88 (m, 24H), 3.58 (d, J=13 Hz, 6H),3.78-3.88 (m, 12H), 4.01-4.11 (m, 12H), 4.84 (d, J=13 Hz, 6H), 6.87 (s,12H); ¹³C NMR (100 MHz, C₂D₂Cl₄, 298 K): δ=26.8, 29.7, 29.9, 30.1, 30.2,36.9, 68.7, 114.5, 130.0, 131.9, 144.3, 145.8, 147.0, 147.4, 149.2;HR-MS (ESI): calcd for C₁₈₄H₁₆₈O₁₂ ⁺ [M]⁺, m/z 2569.2536; found, m/z2569.2704.

Accordingly, unlike complex C₆₀ CTV1, the C₇₀ CTV1 could be purifiedchromatographically, and thus may be called as a hemicarceplex. Anelectrospray ionization (ESI) mass spectrum of the purified C₇₀ CTV1revealed intense peaks at m/z 2569.3 corresponding to the ions [C₇₀CTV1]⁺. The good matches between the observed and calculated isotopepatterns for the ion support the successful synthesis of thehemicarceplex C₇₀ CTV1.

The ¹H NMR and ¹³C NMR spectra of the purified C₇₀ CTV1 hemicarceplex isshown in FIGS. 13D and 14D. In FIG. 14D, the ¹³C NMR spectrum of theisolated hemicarceplex C₇₀ CTV1 displays all five signals belonging toC₇₀, shifted upfield by 0.6-1.2 ppm relative to those of the free C₇₀(FIG. 14C), suggesting encapsulation of spheroidal C₇₀ within the cavityof CTV1.

Synthesis of C₇₀⊙CTV2 Hemicarceplex C₇₀⊙CTV2 hemicarceplex wassynthesized by the following steps. First, CTV2 (40 mg, 23.6 μmol) andC₇₀ (40 mg, 48 μmol) were mixed in CHCl₂CHCl₂ (2 mL) and stirred at 60°C. for 2 days. Then, the residue was purified chromatographically (SiO₂;CS₂ then CH₂Cl₂/hexanes, 4:1) to afford C₇₀⊙CTV2 hemicarceplex as ablack solid (28.6 mg, 46%). The ¹H NMR and ¹³C NMR spectra of thepurified C₇₀⊙CTV2 hemicarceplex is shown in FIGS. 15A and 15B.

An electrospray ionization (ESI) mass spectrum of the purified C₇₀⊙CTV2revealed intense peaks at m/z 2528.2144 corresponding to the ions[C₇₀⊙CTV2+H]⁺.

Comparing CTV1 and CTV2, since the carbon number of three alkyl chainsbetween two cyclotriveratrylenes of CTV2 were decreased from 12 to 11,the size of the inner space and openings of CTV2 were both reduced, too.However, complex C₆₀⊙CTV2 still not stable enough to bechromatographically isolated in pure, thus, cannot be considered as ahemicarceplex. C₇₀⊙CTV1 and the C₇₀⊙CTV2 may be purifiedchromatographically, and thus may be called as hemicarceplex.

All related spectral data of the purified C₇₀ CTV2 hemicarceplex areprovided below. Mp: >300° C. (dec.); ¹H NMR (400 MHz, CDCl₃, 298 K):δ=1.12-1.50 (m, 90H), 1.72-1.88 (m, 26H), 3.56 (d, J=13.6 Hz, 6H),3.71-3.85 (m, 12H), 3.99-4.07 (m, 12H), 4.84 (d, J=13.6 Hz, 6H), 6.83(s, 6H), 6.86 (s, 6H); ¹³C NMR (100 MHz, CDCl₃, 298 K): δ=26.4, 27.0,29.2, 29.7, 29.8, 29.9, 30.0, 30.1, 30.4, 31.1, 37.0, 68.8, 68.9, 113.9,114.3, 130.2, 132.1, 132.2, 144.6, 146.1, 147.2, 147.3, 147.4, 149.4;HR-MS (ESI): calcd for C₁₈₄H₁₆₈O₁₂ ⁺ [M+H]⁺, m/z 2528.2066 found, m/z2528.2144.

Synthesis of C₆₀⊙CTV3 Hemicarceplex C₆₀⊙CTV3 hemicarceplex wassynthesized by the following steps. First, CTV3 (10 mg, 6.07 μmol) andC₆₀ (10 mg, 13.9 μmol) were mixed in CHCl₂CHCl₂ (2 mL) and stirred at50° C. for 20 h. Then, the residue was purified chromatographically(SiO₂; CS₂ then CH₂Cl₂/hexanes, 4:1) to afford C₆₀⊙CTV3 hemicarceplex asa black solid (4.3 mg, 30%). The ¹H NMR and ¹³C NMR spectra of thepurified C₆₀⊙CTV3 hemicarceplex are shown in FIGS. 16A and 16B.

Comparing CTV2 and CTV3, since the carbon number of three alkyl chainsbetween two cyclotriveratrylenes of CTV3 were further decreased from 11to 10, the size of the inner space and openings of CTV3 was furtherreduced, too. Thus, it appeared that the more sizable C₇₀ is not capableto enter the cavity of CTV3 but the smaller C₆₀ can form stablehemicarceplex C₆₀⊙CTV3 with CTV3.

All related spectral data of the purified C₆₀ CTV3 hemicarceplex areprovided below. ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.29-1.53 (m, 84H),1.77-1.93 (m, 24H), 3.44 (d, J=13.6 Hz, 6H), 3.66-3.86 (m, 12H),3.91-4.07 (m, 12H), 4.69 (d, J=14 Hz, 6H), 6.69 (s, 6H), 6.71 (s, 6H);¹³C NMR (200 MHz, CDCl₃, 298 K): δ=25.8, 27.0, 28.3, 28.8, 29.1, 29.2,30.1, 30.8, 31.0, 37.0, 68.7, 68.8, 114.1, 114.2, 131.9, 132.0, 142.1,147.3, 147.4; HR-MS (ESI): calcd for C₁₆₈H₁₅₆O₁₂ ⁺ [M]⁺, m/z 2365.1597found, m/z 2365.1649.

As C₇₀ CTV1 and C₇₀ CTV2, C₆₀ CTV3 could also be purifiedchromatographically, and thus may be called as hemicarceplex. Anelectrospray ionization (ESI) mass spectrum of the purified C₆₀ CTV3revealed intense peaks at m/z 2365.1649 corresponding to the ions [C₆₀CTV3]⁺.

Synthesis of Sc₃N@C₈₀⊙CTV4 Hemicarceplex

Sc₃N@C₈₀⊙CTV4 hemicarceplex was synthesized by the following steps.First, equimolar of the CTV4 and Sc₃N@C₈₀ were mixed in CDCl₂CDCl₂ toform an equimolar mixture (6 mM). Then, the mixture stirred at roomtemperature for 20 hours to form Sc₃N@C₈₀⊙CTV4 hemicarceplex. The ¹H NMRspectrum of the purified Sc₃N@C₈₀⊙CTV4 hemicarceplex is shown in FIG.17. An electrospray ionization (ESI) mass spectrum of the purifiedSc₃N@C₈₀⊙CTV4 revealed intense peaks at m/z 3020.1055 corresponding tothe ions [Sc₃N@C₈₀⊙CTV4+H]⁺.

All related spectral data of the purified Sc₃N@C₈₀⊙CTV4 hemicarceplexare provided below. ¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.11-1.45 (m,42H), 1.77-2.07 (m, 42H), 2.62 (s, 12H), 3.50 (d, J=13.6 Hz, 6H),3.71-3.80 (m, 6H) 3.84-3.91 (m, 6H), 3.96-4.04 (m, 12H), 4.23-4.36 (m,12H), 4.74 (d, J=13.2, 6H), 6.74 (s, 12H); HR-MS (ESI): calcd forC₁₉₄H₁₅₇NO₂₄Sc₃ [M+H]⁺, m/z 3020.1745; found, m/z 3020.1055.

The Formation of C₆₀⊙CTV5 and C₇₀⊙CTV5 Complexes

C₆₀ ⊙CTV5 and C₇₀⊙CTV5 complexes were synthesized by mixing equimolar ofthe CTV5 and purified C₆₀ and C₇₀ in CDCl₂CDCl₂, respectively.

The ¹H NMR spectra of the equimolar mixture of CTV5 to C₆₀ and C₇₀ arerespectively shown in FIGS. 18A and 18B. In FIGS. 18A and 18B, thedescriptors (c) and (uc) respectively refer to the complexed anduncomplexed states of the corresponding components.

Comparing CTV2 and CTV5, the atom numbers of the three alkyl chainsbetween two cyclotriveratrylenes were the same (11 atoms), but the atomnumbers of the other three chains were increase from 12 to 14, the sizeof the openings of the CTV5 was increased. Therefore, C₆₀ and C₇₀ couldboth enter the inner space of the CTV5 but the complexes formed are notstable enough to be isolated through column chromatography and cannot becalled as hemicarceplexes.

The Formation of C₆₀⊙CTV6 Complexes C₆₀⊙CTV6 complexes were synthesizedby mixing equimolar of the CTV6 and C₆₀ in CDCl₂CDCl₂. The ¹H NMRspectra of the equimolar mixture of CTV6 and C₆₀ are shown in FIG. 19B.For comparison, the ¹H NMR spectrum of CTV6 is also shown in FIG. 19A.

In FIG. 19B, the ¹H NMR spectrum of the 4 mM equimolar mixture of C₆₀and CTV6 shows a new set of signals corresponding to the C₆₀ CTV6complex.

Comparing CTV6 and CTV5, the atom numbers of the three alkyl chainsbetween two cyclotriveratrylenes were decreased from 11 to 10, but theatom numbers of the other three chains remains the same (14 atoms), thesize of the molecular openings of the CTV6 was, thus, reduced.Therefore, C₆₀ but not C70 could enter the inner space of the CTV6,however, the complexes formed are not stable enough to be isolatedthrough column chromatography.

Synthesis of C₇₆⊙CTV7 and C₇₈⊙CTV7 Hemicarceplexes

C₇₆⊙CTV7 and C₇₈⊙CTV7 hemicarceplexes were synthesized by the followingsteps. First, CTV7 (510 mg, 288 mmol) and high-order fullerene mixture(680 mg) were mixed in CHCl₂CHCl₂ (34 mL) and stirred at 35° C. for 40h. Then, the residue was purified chromatographically (SiO₂; CS₂ thenCH₂Cl₂/hexanes, 4:1) to afford C₇₆⊙CTV7 and C₇₈®CTV7 hemicarceplexes asa black solid (361 mg). The ¹H NMR spectra of the purified C₇₆⊙CTV7 andC₇₈®CTV7 hemicarceplex is shown in FIG. 20.

HR-MS of C₇₆⊙CTV7 (ESI): calcd for C₁₉₃H₁₇₅O₁₂ ⁺ [M+H]⁺, m/z 2684.3084,found, m/z 2684.3147. HR-MS of C₇₈⊙CTV7 (ESI): calcd for C₁₉₅H₁₇₅O₁₂ ⁺[M+H]⁺, m/z 2708.3084, found, m/z 2708.3198.

Synthesis of C₈₄⊙CTV8 Hemicarceplex

C₈₄⊙CTV8 hemicarceplex was synthesized by the following steps. First,CTV8 (243 mg, 134 mmol) and high-order fullerene mixture obtained fromprevious C₇₆ and C₇₈ extraction (243 mg) were mixed in CHCl₂CHCl₂ (45mL) and stirred at 30° C. for 16 h. Then, the residue was purifiedchromatographically (SiO₂; CS₂ then CH₂Cl₂/hexanes, 4:1) to affordC₈₄⊙CTV8 hemicarceplex as a black solid (112 mg). The ¹H NMR of thepurified C₈₄⊙CTV8 hemicarceplex is shown in FIG. 21. HR-MS of C₈₄⊙CTV8(ESI): calcd for C₂₀₄H₁₈₀O₁₂ ⁺ [M]⁺, m/z 2821.3475, found, m/z2821.3499.

Synthesis of fullerenes⊙CTV9 Complexes

Fullerenes⊙CTV9 complexes were formed by mixing CTV9 (3 mg) andhigher-order fullerene extract (3 mg) in CDCl₂CDCl₂ (0.5 mL) at roomtemperature. The appearance of several new set of signals for thecomplexed host CTV9 in the ¹H NMR spectrum in FIG. 22 similar to theones observed in the case of the above fullerene-complexed CTV hosts,suggested the formation of the fullerenes⊙CTV9 complex under thiscondition.

Synthesis of C₇₀⊙CTV10 Complex

C₇₀⊙CTV10 complex was formed by mixing CTV10 (2.8 mg) and C₇₀ (1.2 mg)in CDCl₂CDCl₂ (0.4 mL) at room temperature. The appearance of a new setof signals for the complexed host CTV10 in the ¹H NMR spectrum in FIG.23 similar to the ones observed in the case of the abovefullerene-complexed CTV hosts, suggested the formation of the C₇₀⊙CTV10complex under this condition.

Synthesis of C₆₀⊙CTV11 Hemicarceplex

C₆₀⊙CTV11 hemicarceplex was synthesized by the following steps. First,CTV11 (40 mg, 26 μmol) and C₆₀ (40 mg, 56 μmol) was ball-milled at roomtemperature for 1 h and the solid residue was heated under vacuum at250° C. for 15 h. The resulting solid was purified chromatographically(SiO₂; 082 then CH₂Cl₂/hexane, 4:1) to afford C₆₀⊙CTV11 as a brown solid(22 mg, 38%). The ¹H NMR and ¹³C NMR spectra of the purified C₆₀⊙CTV11hemicarceplex are shown in FIGS. 24A and 24B, respectively. All relatedspectral data are listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.20-1.50 (m, 60H), 1.60-1.79 (m,24H), 1.80-1.91 (m, 12H), 3.44 (d, J=13.6 Hz, 6H), 3.66-3.75 (m, 12H),4.05-4.07 (m, 12H), 4.68 (d, J=13.6 Hz, 6H), 6.70 (s, 12H); ¹³C NMR (100MHz, CDCl₃, 298 K): δ=27.2, 30.2, 30.8, 30.9, 37.1, 68.6, 114.9, 132.1,142.0, 147.7; HR-MS (ESI): calcd for C₁₆₂H₁₄₄O₁₂ ⁺ [M]⁺, m/z 2281.0658;found, m/z 2281.0689.

Synthesis of C₆₀⊙CTV12 Hemicarceplex C₆₀⊙CTV12 hemicarceplex wassynthesized by the following steps. First, CTV12 (30 mg, 19 pmole) andC₆₀ (50 mg, 0.069 mmole) was ball-milled at room temperature for 1 h andthe solid residue was heated under vacuum at 240° C. for 12 h. Theresulting solid was purified chromatographically (SiO₂; CS₂ thenCH₂Cl₂/hexane, 4:1) to afford C₆₀⊙CTV12 as a brown solid (27 mg, 61%).The ¹H NMR and ¹³C NMR spectra of the purified C₆₀⊙CTV12 hemicarceplexare shown in FIGS. 25A and 25B, respectively. All related spectral dataare listed below.

¹H NMR (400 MHz, CDCl₃, 298 K): δ=1.28-1.52 (m, 78H), 1.57-1.93 (m,24H), 3.43 (d, J=13.6 Hz, 6H), 3.65-3.77 (m, 12H), 3.95-4.08 (m, 12H),4.68 (d, J=13.6, 6H), 6.70 (s, 12H); ¹³C NMR (100 MHz, CDCl₃, 298 K):δ=26.0, 26.9, 28.4, 29.0, 29.3, 29.6, 30.0, 30.8, 30.9, 37.0, 68.3,68.8, 114.0, 114.4, 131.8, 132.0, 142.1, 147.3, 147.4; HR-MS (ESI):calcd for C₁₆₅H₁₅₀O₁₂Na⁺ [M+Na]⁺, m/z 2346.1020; found, m/z 2346.0946.

Kinetic Data of C₆₀ CTV1 and C₇₀ CTV1

Complexation of the CTV1 with C₆₀

Experiments were performed in CDCl₂CDCl₂ using an equimolar (3 mM)mixture of the CTV1 and C₆₀ at 25° C.

In this experiment, a simplified second-order rate equation (1) shownbelow was used to calculate an association rate constant (k_(a)) offorming C₆₀ CTV1 complex at the early stage of complexation.

k _(a)=(1/[A _(t)]−1/[A ₀])/t={1/([A ₀ ]−[P _(t)])−1/[A ₀ ]}/t  (1)

The initial concentration of free CTV, [A₀], and the free C₆₀, [B₀],were both 3 mM. [A_(t)] is the concentration of the free CTV1 at time t,and [P_(t)] is the concentration of the C₆₀ CTV1 complex at time t.[A_(t)] and [P_(t)] were determined based on the integration values ofthe signals at δ 6.80 (H_(p), s, 12H) and δ 6.70 (H_(p′), s, 12H),respectively. [A_(t)] could also be determined based on [A₀]-[P_(t)].Accordingly, based on a plot of 1/[A_(t)]-1/[A₀] against t (s) at 298 K,the association rate constant (k_(a)) was obtained by calculating theslope of the plot. The obtained association rate constant (k_(a)) was1.68×10⁻¹ M-s⁻¹.

The half-life time of the complexation reaction (t_(1/2)) was given byequation (2) below. The calculated half-life time of the complexationreaction (t_(1/2)) was 33.1 min.

t _(1/2)=1/(k _(a) [A ₀])  (2)

The value of ΔG^(‡) (kcal mol⁻¹) was calculated using the relationshipshown in equation (3) below, where R, h, and k_(B) are the gas, Planck,and Boltzmann constants, respectively. The calculated ΔG^(‡) was 18.49kcal mol⁻¹.

ΔG ^(‡) =−RT ln(kh/k _(B) T)  (3)

The equilibrium constant (K_(a)) of forming C₆₀ CTV1 complex at 25° C.was also determined. ¹H NMR spectrum (400 MHz, CDCl₂CDCl₂, 298 K) of anequimolar (C_(M)=3 mM) mixture of C₆₀ and the CTV1 after heating at 298K for 7 days was used to determine the equilibrium constant (K_(a)) offorming C₆₀ CTV1 complex. The integration values for the signals of thefree (I_(f), 6.8 ppm) and complexed (I_(c), 6.7 ppm) species are 1.016and 0.843, respectively. Therefore, the equilibrium constant (K_(a)) offorming C₆₀ CTV1 complex was determined by using equation (4) below tobe 506 M⁻¹.

K _(a) =I _(c)(f+I _(c))/(I _(f) ² C _(M))  (4)

Dissociation of the Hemicarceplex C₇₀ CTV1

The dissociation experiments were performed using constantconcentrations of the hemicarceplex C₇₀ CTV1 (3 mM) in CDCl₂CDCl₂,ds-toluene, CDCl₃, CDCl₃/CD₃CN (95:5 and 90:10 in volume ratio), andCDCl₃/CD₃NO₂ (95:5 and 90:10 in volume ratio). ¹H NMR spectra wererecorded at regular intervals during the experiment. Because of the poorsolubility of the CTV1 in toluene, trichloroethene was added as aninternal standard to determine the concentration of the hemicarceplexduring the dissociation.

The reverse reaction may be ignored during the early stages of thefirst-order decomplexation event. Therefore, using the first-order ratelaw shown in equation (5) below, the dissociation rate constants (k_(d))were determined at the early stages of decomplexation from the slopes ofthe straight lines in the plots of ln([A₀]/[A_(t)]) against t (s) at 25°C. The concentration of the C₇₀ CTV1 hemicarceplex, [P_(t)], wasdetermined from the integration of signals at ca. δ 6.90 (H_(p), s,12H).

k _(d)=ln([P ₀ ]/[P _(t)])/t  (5)

The half-life time of the decomplexation reaction (t_(1/2)) was given byequation (6) below.

t _(1/2)=ln(2/k _(d))  (6)

The values of ΔG^(‡) (kcal mol⁻¹) were also calculated using therelationship shown in equation (3).

The obtained dissociation rate constants (k_(d)), ΔG^(‡), and t_(1/2)are listed in Table 1 below. From the dissociation rate constants(k_(d)) listed in Table 1, it may be known that the dissociation rateconstant was decreased as the polarity of the solvent system wasincreased from CDCl₂CDCl₂ to CDCl₃/CD₃CN (90:10). This is because of thelipophilicity of C₇₀, which make the dissociation state of thehemicarceplex C₇₀ CTV1 to be more unstable.

TABLE 1 The obtained dissociation rate constants (k_(d)), ΔG^(‡), andt_(1/2) for the hemicarceplex C₇₀ CTV1 dissociated in various solventsystem. ΔG^(‡) Solvent k_(d) (s⁻¹) t_(1/2) (h) (kcal mol⁻¹) d₈-toluene6.5 ± 0.7 × 10⁻⁵  3.0 ± 0.3 23.2 ± 0.1 CDCl₂CDCl₂ 6.3 ± 0.7 × 10⁻⁶ 30.6± 3.3 24.6 ± 0.1 CDCl₃ 5.1 ± 0.5 × 10⁻⁶ 37.8 ± 3.3 24.7 ± 0.1CDCl₃/CD₃NO₂ (95:5) 5.0 ± 0.5 × 10⁻⁶ 38.5 ± 3.8 247.8 ± 0.1  CDCl₃/CD₃CN(95:5) 4.3 ± 0.4 × 10⁻⁶ 44.8 ± 4.0 24.7 ± 0.1 CDCl₃/CD₃NO₂ (90:10) 3.6 ±0.3 × 10⁻⁶ 53.5 ± 4.0 25.0 ± 0.1 CDCl₃/CD₃CN (90:10) 3.2 ± 0.3 × 10⁻⁶60.2 ± 4.9 24.9 ± 0.1

Similarly, the relatively rapid dissociation of the hemicarceplex C₇₀CTV1 in toluene-d₈ was because of C₇₀ stabilized more in the dissociatedstate than in the complex. Moreover, because of the poor solubility ofthe CTV1 in toluene-d₈, a white solid precipitated from the red solutionduring dissociation of the hemicarceplex C₇₀ CTV1 in this solvent.Correspondingly, the ¹H NMR spectra revealed a gradual decrease in theintensity of signals belonging to the hemicarceplex, but without theappearance of any signals for the free CTV1. Accordingly, the relativelyrapid dissociation rate and the precipitation of the free CTV1 from thered solution of the hemicarceplex C₇₀ CTV1 in toluene-d₈ suggested thattoluene would be a good choice of solvent for dissociating thehemicarceplex into its free components on a practical scale.

The equilibrium constant (K_(a)) of forming C₇₀ CTV1 complex at 25° C.was also determined. ¹H NMR spectrum (400 MHz, CDCl₂CDCl₂, 298 K) of themixture obtained from the decomplexation of C₇₀⊙CTV1 (C_(M)=3 mM) at 298K after 10 days was used to determine equilibrium constant (K_(a)) offorming C₇₀ CTV1 complex. The integration values for the signals of thefree (I_(f), 6.8 ppm) and complexed (I_(c), 6.9 ppm) species are 0.324and 1.000, respectively. Therefore, the equilibrium constant (K_(a)) offorming C₇₀ CTV1 complex was determined by using equation (4) above tobe 4204 M⁻¹. In addition, the association rate constant (k_(a)) wasdetermined to be 0.026 M⁻¹ s⁻¹. The determination methods were similarto the methods mentioned for the C₆₀ CTV1 complex above, and henceomitted here.

The Release of the Fullerenes Incarcerated in C₇₆⊙CTV7 and C₇₈⊙CTV7Hemicarceplexes

The C₇₆⊙CTV7 and C₇₈⊙CTV7 hemicarceplexes (188 mg) were dissolved intoluene (20 mL) and heated at 50° C. for 16 h. The toluene solution wasremoved via pipette after centrifugation. Another charge of toluene (5mL) was added to wash the white solid and then the mixture wascentrifuged again. The residue obtained after concentrating the combinedtoluene phases was suspended in CH₂Cl₂ (10 mL), in which thehemicarceplex mixtures are highly soluble, forming a black precipitateof fullerene mixtures, which were collected through centrifugation. Thefullerene mixtures were then resuspended in CH₂Cl₂ (5 mL), centrifuged,separated from the solvent, and dried (43 mg).

The purity was determined through HPLC analysis. The HPLC analysisresults were shown in FIG. 26, which not only supported that thehemicarcerplexes do have C₇₆ and C₇₈ incarcerated but also suggested theformation of C₇₀⊙CTV7, C₈₂⊙CTV7, C₈₄⊙CTV7 and C₈₆⊙CTV7 as the minorproducts. The results indicated that selective isolation of C₇₆ and C₇₈from high-order fullerene mixture may be achieved by using CTV7 as theentrapping host.

The Release of the Incarcerated C₈₄ from C₈₄⊙CTV8 Hemicarceplexes

The C₈₄⊙CTV8 hemicarceplexes (122 mg) were dissolved in CS₂ (10 mL) atroom temperature and stirred for 16 h. The CS₂ solution was removed viapipette after centrifugation. Another charge of CS₂ (5 mL) was added towash the white solid and then the mixture was centrifuged again. Theresidue obtained after concentrating the combined toluene phases wassuspended in CH₂Cl₂ (10 mL), in which the hemicarceplex mixtures arehighly soluble, forming a black precipitate of fullerene mixtures, whichwere collected through centrifugation. The fullerene mixtures were thenresuspended in CH₂Cl₂ (5 mL), centrifuged, separated from the solvent,and dried (30 mg).

The purity was determined through HPLC analysis. The HPLC analysisresults were shown in FIG. 27, which not only supported that thehemicarcerplexes do have C₈₄ incarcerated but also suggested theformation of C₇₀⊙CTV8, C₇₆⊙CTV8, C₇₈⊙CTV8, C₈₂⊙CTV8 and C₈₆⊙CTV8 as theminor products. The results indicated that selective isolation of C₈₄from high-order fullerene mixture may be achieved by using CTV8 as theentrapping host.

Isolating Fullerenes from Fullerene Extracts by Using Fullerene CTVHemicarceplexes

Fullerenes or derivatives thereof may be isolated from their mixtures inhigh purity through the following steps: (1) selectively generating afullerene⊙CTV hemicarceplex in solution, (2) isolating the fullerene⊙CTVhemicarceplexes by column chromatography, and (3) dissociating thefullerene⊙CTV hemicarceplexes to release the pure fullerenes. FIG. 28 isa process flow diagram of isolating fullerenes without usingcrystallization or HPLC.

In the step 1410 of FIG. 28, fullerene CTV hemicarceplexes has to beformed first. In step 1420, the fullerene CTV hemicarceplexes are thenisolated by using column chromatography. In step 1430, the isolatedfullerenes are obtained by dissociating the fullerene CTVhemicarceplexes. The related details of each step are described below.

In step 1410 of FIG. 28, fullerene CTV hemicarceplexes are formed bymixing a CTV host and a fullerene mixture, such as a fullerene extract,in a first solvent at a first temperature to form a first mixturesolution. Then, the first mixture solution is concentrated under areduced pressure to obtain a first solid residue.

The first solvent can dissolve both fullerenes and CTV host and do nothave strong tendency to enter and compete with fullerenes in occupyingthe inner space of the CTV host. For example, the first solvent canmajorly contain CS₂, CH₂Cl₂, CHCl₃ or CHCl₂CHCl₂ but is not limitedthereto.

The formation of fullerene CTV hemicarceplexes may be inspected byeither ¹H or ¹³C NMR, such as those NMR spectra shown in FIGS. 13-17discussed above. Accordingly, the lowest first temperature has to besufficiently high to see that new NMR signals corresponding to thefullerene CTV hemicarceplexes appear within few hours. For example, thefirst temperature may be room temperature to 60° C., such as 40° C., butis not limited thereto.

Moreover, the needed reaction time can also be determined by either 1Hor ¹³C NMR. When the new NMR signals corresponding to the fullerene CTVhemicarceplexes grow to reach a maximum strength, the reaction may bestopped.

Next, a second solvent is added to the first solid residue to form asuspended solution. Then, the suspended solution is filtered to obtainfiltrate of the suspended solution.

The CTV host and the fullerene CTV hemicarceplexes have bettersolubility in the second solvent than the free fullerenes. Therefore,most of the free fullerenes may be filtered off, and the filtratecontains the fullerene CTV hemicarceplexes. For example, the secondsolvent can majorly contain CH₂Cl₂, CHCl₃ or CHCl₂CHCl₂, but is notlimited thereto.

In step 1420 of FIG. 28, the filtrate of the suspended solution in step1410 is concentrated and then loaded onto a column of silica gel toprepare for a subsequent column chromatography. Then, a third solvent, afourth solvent, and a fifth solvent were sequentially used to elute thefree fullerenes, fullerene⊙CTV hemicarceplexes, and free CTV hosts fromthe column. Since the polarity of the free fullerenes, fullerene⊙CTVhemicarceplexes, and free CTV hosts are generally in an increasingorder, the polarity of the third solvent, the fourth solvent, and thefifth solvents for eluting the molecules above are better also generallyin an increasing order.

Accordingly, since the third solvent is used to remove any uncomplexedand/or dissociated fullerenes from the column, the third solvent has tobe capable of dissolving free fullerenes. For examples, the thirdsolvent can majorly contain CS₂, benzene, toluene or dichlorobenzene butis not limited thereto.

The fourth solvent is used to isolate the fullerene CTV hemicarceplexesfrom the column. Therefore, the fourth solvent has to be capable ofdissolving the fullerene CTV hemicarceplexes. For example, the fourthsolvent can majorly contains CH₂Cl₂ or CHCl₃, such as CH₂Cl₂ and hexanemixed in a volume ratio of 3:2, but is not limited thereto.

The fifth solvent is used to elute the free CTV host from the column, sothat the free CTV host may be recover for the next use. Therefore, thefifth solvent has to be capable of dissolving the free CTV host. Forexample, the fifth solvent can majorly contains CH₂Cl₂ or CHCl₃, such asCH₂Cl₂ and MeOH mixed in a volume ratio of 49:1, but is not limitedthereto.

In step 1430 of FIG. 28, the portion of the eluate containing thefullerene⊙CTV hemicarceplexes is concentrated, and a sixth solvent isthen added to dissociate the fullerene CTV hemicarceplexes at a secondtemperature. In the best scenario, free fullerenes have good solubilityin the sixth solvent, and the CTV host has a poor solubility in thesixth solvent. Therefore, the released fullerenes and fullerene CTVhemicarceplexes are still dissolved in the sixth solvent, but the freeCTV host is precipitated as solid. Otherwise, the dissociated freefullerenes can still be separated from free cage and the hemicarceplexesby chromatographic methods. Accordingly, the sixth solvent can majorlycontain CS₂, CH₂Cl₂, CHCl₃, CHCl₂CHCl₂, benzene, toluene, ordichlorobenzene, for example, but is not limited thereto.

Since the dissociation reaction is the reverse reaction thehemicarceplexe formation reaction, the dissociation reaction may alsoneed heating. The lowest temperature for the second temperature also maybe determined by NMR spectra when the NMR signals corresponding to thefullerene CTV hemicarceplexes decrease within few hours. For examples,the second temperature may be higher than room temperature, such as 30°C. to 80° C., but is not limited thereto.

Next, the solution of the sixth solvent was concentrated, and a seventhsolvent is then added. For separating the released fullerenes andfullerene CTV hemicarceplexes, the released fullerenes have a poorsolubility in the seventh solvent, and the fullerene CTV hemicarceplexeshave a good solubility in the seventh solvent. Therefore, the seventhsolvent can majorly contain CH₂Cl₂, or CHCl₃, for example, but is notlimited thereto.

Since the seventh solvent has poor solubility for the free fullerenes,the free fullerenes are precipitated. Hence, a simple filtering step canobtain the free fullerenes.

Experiment 1 Using CTV1 to Isolate 070 from Fullerene Extract: SmallScale

(1) Forming C₇₀⊙CTV1 Hemicarceplex:

The CTV1 (50 mg) and the fullerene extract above (300 mg, purchased fromSES Research) were dissolved in CHCl₂CHCl₂ (5 mL) and stirred at varioustemperatures for various periods of time for Examples 1-6. The organicsolvent was removed under reduced pressure and the residue was dissolvedin CH₂Cl₂ (40 mL). After filtration, the solvent was evaporated underreduced pressure to obtain various amounts of solid for Examples 1-6.The related data above were listed in Table 2 below.

TABLE 2 Related data of forming C₇₀⊙CTV1 hemicarceplex Examples Stirringtemp. (° C.) Stirring time (h) Solid amount (mg) 1 40 16 86.4 2 40 16101.1 3 40 16 111.2 4 50 16 72.8 5 40 40 91.4 6 40 16 98.4

(2) Using Column Chromatography to Isolate C₇₀⊙CTV1 Hemicarceplex:

The obtained solid above was purified through column chromatography (5 gof SiO₂). The eluents of CS₂, CH₂Cl₂/hexane (3:2 in volume ratio) andCH₂Cl₂/MeOH (49:1 in volume ratio) were sequentially used tosequentially elute free fullerenes, C₇₀⊙CTV1, and free CTV1 from thecolumn. The eluate portions of the CH₂Cl₂/hexanes (3:2 in volume ratio)of Examples 1-6 were then respectively evaporated to obtain variousamounts of C₇₀⊙CTV1. The using amounts of each eluent and the obtainedamounts of C₇₀⊙CTV1 are all listed in Table 3 below.

TABLE 3 Related data of column chromatography Eluents (mL) CH₂Cl₂/hexaneCH₂Cl₂/MeOH C₇₀⊙CTV1 Examples CS₂ (3:2) (49:1) (mg) 1 50 250 100 37.2 250 250 50 33.1 3 50 400 50 32.2 4 50 200 50 30.0 5 50 250 50 38.4 6 50250 50 37.3

(3) Obtaining C₇₀ by Dissociating C₇₀⊙CTV1

The obtained C₇₀⊙CTV1 hemicarceplex was then dissolved in toluene (4 mL)and heated at a temperature for 12 h to dissociate the C₇₀⊙CTV1hemicarceplex. The toluene solution was centrifuged to yield uppertoluene solution and white precipitate. The upper toluene solutioncontaining the free C₇₀ was removed via pipette. Another charge oftoluene (5 mL) was added to wash the white solid of CTV1 to wash downthe residue free C₇₀ from the white solid. Then, the two toluenesolutions were mixed and centrifuged again to take the upper toluenesolution. The white solid was recycled as the free CTV1.

The residue obtained after concentrating the combined toluene solutionswas suspended in CH₂Cl₂ (5 mL) again to dissolve the highly solubleC₇₀⊙CTV1 hemicarceplex. However, the free C₇₀ formed red precipitate inthe CH₂Cl₂. Therefore, the C₇₀ red precipitate in the CH₂Cl₂ wasobtained by centrifuging the CH₂Cl₂ suspension and then drying, and theblack CH₂Cl₂ solution was then dried to recycle C₇₀⊙CTV1 hemicarceplex.

The composition of the purchased fullerene extract and the purity of C₇₀was determined through HPLC analysis (Cosmosil-packed 5PBB analyticalcolumn, 4.6×250 mm; mobile phase, toluene; UV detection, 285 nm; elutionrate, 1 mL min⁻¹). Accordingly, the compositions of the purchasedfullerene extract and the purity of C₇₀ were determined by dividing theintegration value of the corresponding signal by the total integrationvalues of the C₆₀, C₇₀, C₇₆, C₇₈, and C₈₄ signals.

Accordingly, the dissociation temperatures and the obtained amounts andpurity of C₇₀ for Examples 1-6 were listed in Table 4, and the amountsof the recycled C₇₀⊙CTV1 hemicarceplex and recovered CTV1 for Examples1-6 were listed in Table 5. The compositions of the purchased fullereneextract and the purified C₇₀ of Example 1 are listed in Table 6 below.

TABLE 4 Related data of dissociating C₇₀⊙CTV1 hemicarceplex DissociationPurity of Examples temp. (° C.) Obtained C₇₀ (mg) obtained C₇₀ (%) 1 307.1 99.1 2 30 6.5 99.0 3 30 6.7 99.1 4 30 8.2 93.5 5 30 8.0 96.4 6 408.3 96.7

TABLE 5 Recovered amounts of the C₇₀⊙CTV1 hemicarceplex and CTV1Examples C₇₀⊙CTV1 (mg) CTV1 (mg) 1 15.0 30.3 2 12.8 30.5 3 12.3 30.6 4 —27.6 5 — 30.4 6 — 31.6

TABLE 6 Analyzing compositions of the purchased fullerene extract andthe purified C₇₀ of Examples 1-6 by HPLC Examples C₆₀ (%) C₇₀ (%) C₇₆(%) C₇₈ (%) C₈₄ (%) 1 0.03 99.1 0.83 0 0 2 0.14 99.0 0.88 0 0 3 0.0399.1 0.90 0 0 4 0.21 93.5 2.75 0.13 0 5 0.35 96.4 2.99 0.27 0 6 0.0796.7 1.66 0.13 0 Fullerene 65.97 24.02 1.75 1.85 2.62 extract

Experiment 2 Using CTV1 to Isolate C₇₀ from Fullerene Extract: LargeScale

After obtaining consistent results when repeating the isolation as shownabove, the scale was increased to ten-fold of the previous small scaleexperiments.

The CTV1 (500 mg) and the fullerene extract (3.0 g) were dissolved inCHCl₂CHCl₂ (50 mL) and stirred at 40° C. for 16 h. The organic solventwas removed under reduced pressure and the residue was dissolved inCH₂Cl₂ (250 mL). After filtration, the solvent was evaporated underreduced pressure to afford a solid (950 mg), which was purified throughcolumn chromatography [SiO₂ (25 g); eluent: CS₂ (250 mL) followed byCH₂Cl₂/hexane, 3:2 (1550 mL), and CH₂Cl₂/MeOH, 49:1 (600 mL)].

The hemicarceplex (366.1 mg) obtained was then dissolved in toluene (20mL) and heated at 30° C. for 12 h. The toluene solution was removed viapipette after centrifugation. Another charge of toluene (20 mL×2) wasadded to wash the white solid and then the mixture was centrifugedagain. The white solid was recycled as the free CTV1. The residueobtained after concentrating the combined toluene phases was suspendedin CH₂Cl₂ (20 mL), in which the hemicarceplex C₇₀⊙CTV1 is highlysoluble, to form a red precipitate of C₇₀, which was collected throughcentrifugation. The solid C₇₀ was then resuspended in CH₂Cl₂ (20 mL×2),centrifuged, separated from the solvent, and dried (72.6 mg). The purityof C₇₀, determined through HPLC analysis, was 99.0%. The black CH₂Cl₂solution was then concentrated to recycle 96.4 mg of the hemicarceplexC₇₀⊙CTV1. The total amount of recovered CTV1 was 360 mg (72% recovery).

The recycled hemicarceplex (96.4 mg) was redissolved in toluene (10 mL)and heated at 30° C. for 12 h. The suspension was centrifuged to affordthe CTV1 as a white precipitate. The organic solution was removed viapipette and concentrated to give a black solid, which was dissolved inCH₂Cl₂ (10 mL) and centrifuged. The solid O₇₀ was then resuspended inCH₂Cl₂ (10 mL×2), centrifuged, separated from the solvent, and dried(6.6 mg). The purity of the C₇₀, determined through HPLC analysis, was92.6%. The black CH₂Cl₂ solution was concentrated to obtain 78.6 mg ofthe recycled hemicarceplex C70⊙CTV1. The amount of recycled CTV1 was13.8 mg (26% recovery).

Accordingly, the compositions of the large-scale purified C₇₀ obtainedin the first round and second round of isolation process and thepurchased fullerene extract are listed in Table 7 below. The percentagesof each component were determined by the HPLC method mentioned in thesmall scale experiment above.

TABLE 7 Analyzing the compositions of the large-scale purified C70obtained in the first round and second round of isolation process byHPLC composition C₆₀ (%) C₇₀ (%) C₇₆ (%) C₇₈ (%) C₈₄ (%) First round0.03 99.0 0.90 0.10 0 Second round 0.05 92.6 6.00 0.65 0 Fullereneextract 65.97 24.02 1.75 1.85 2.62

Accordingly, the isolated C₇₀ in the first round isolation process wasnot only in approximately 10 times the amount (72.6 mg) of the previoussmall scale experiments, but also in similar purity (99.0%) to theprevious small scale experiments. Thus, the amount of C₇₀ isolated in asingle purification cycle should be scalable to even greater levels if agreater amount of CTV1 is applied.

In this large-scale experiment, the total amount of the CTV1 that werecovered after chromatography and precipitation from toluene was 360 mg(72% recovery). Concentrating the CH₂Cl₂ phase obtained afterdissociation of the hemicarceplex under reduced pressure allowedrecycling of 96 mg of the hemicarceplex C₇₀⊙CTV1 (26% recovery,containing 64 mg of CTV1). Therefore, the mass loss of the CTV1throughout the whole isolation process was approximately 15%. Becausethe dissociation of the hemicarceplex did not require competing guests,the recycled CTV1 could be used directly in a subsequent isolation cyclewithout the need for any specific treatment or purification process.

In the second round of isolation process, dissociation of the recycledhemicarceplex under similar conditions afforded C₇₀ in 92.6% purity(HPLC analysis). Notably, based on HPLC analysis, the C₇₀ isolated usingthis method was only negligibly contaminated with C₆₀ (0.05%); its majorimpurities were C₇₆ (6.00%) and C₇₈ (0.65%). Therefore, the CTV1 appearsto also isolate C₇₆ and C₇₈ from the fullerene extract. Based on HPLCanalysis of the commercial fullerene extract that we tested in thisstudy, the ratio of C₇₆, C₇₈, and C₈₄ was approximately 1:1.1:1.6 (i.e.,C₇₆ was a relatively minor component). Therefore, our CTV1 appears to becapable of kinetically differentiating these three buckyballs throughthe effective formation of the hemicarceplex C₇₆⊙CTV1 under thedeveloped experimental conditions.

Experiment 3 Using CTV1 to Obtain a Mixture of C₇₀, C₇₆ and C₇₈ fromHigh Fullerene Extract

The CTV1 (50 mg) and the high fullerene extract (50 mg; purchased fromMER Corp.) were mixed in CHCl₂CHCl₂ (5 mL) and stirred at 40° C. for 18h. The organic solvent was evaporated under reduced pressure and theresidue was dissolved in CH₂Cl₂ (20 mL). After filtration, the solventwas evaporated under reduced pressure to afford a solid, which waspurified through column chromatography [SiO₂ (8 g); eluent: CS₂ (50 mL)followed by CH₂Cl₂/hexane, 3:2 (400 mL), and CH₂Cl₂/MeOH, 49:1 (100mL)].

The hemicarceplex mixtures (32.0 mg) were obtained and the aboveexperiment was repeated three times and collected hemicarceplex mixture(105 mg) was then dissolved in toluene (5 mL) and heated at 30° C. for 6h. The toluene solution was removed via pipette after centrifugation.Another charge of toluene (5 mL) was added to wash the white solid andthen the mixture was centrifuged again. The white solid was recycled asthe free CTV1.

The residue obtained after concentrating the combined toluene phases wassuspended in CH₂Cl₂ (5 mL), in which the hemicarceplex mixtures arehighly soluble, forming a red precipitate of fullerene mixtures, whichwere collected through centrifugation. The fullerene mixtures were thenresuspended in CH₂Cl₂ (5 mL), centrifuged, separated from the solvent,and dried (4.8 mg). The purity was determined through HPLC analysis. TheHPLC analysis results were listed in Table 8 below. From the HPLCresult, it may be known that the mixture of C₇₀, C₇₆ and C₇₈ may beisolated from the mixture of the high fullerene extract.

TABLE 8 Analyzing the compositions of the purchased high fullereneextract and the purity of the obtained black solid fullerene mixtures byHPLC composition C₆₀ (%) C₇₀ (%) C₇₆ (%) C₇₈ (%) C₈₄ (%) High fullereneextract 4.2 6.8 12.9 14.0 65.8 Obtained fullerene 0 7.2 52.5 40.3 0mixtures

Experiment 4 Using CTV5 to Obtain Mixture of C₇₆ and C₇₈ from Mixture ofC₇₀, C₇₆ and C₇₈

The CTV5 (1.5 mg) and the fullerene mixture [0.75 mg; the one containsonly C₇₀, C₇₆ and C₇₈ obtained from the Experiment 3] were mixed inCHCl₂CHCl₂ (0.4 mL) at 27° C. for 21 h. The organic solvent wasevaporated under reduced pressure to afford a solid, which was purifiedthrough column chromatography [SiO₂ (0.4 g); eluent: CS₂ (2 mL) followedby EA/hexane, 3:7 in volume ratio (10 mL)]. The hemicarceplex mixturewas then dissolved in toluene (0.8 mL) and heated at 50° C. for 40 h.The toluene solution was analyzed by HPLC. The HPLC analysis resultswere listed in Table 9 below. From the HPLC analysis result, it may beknown that the mixture of O₇₆ and C₇₈ may be isolated from the mixtureof C₇₀, C₇₆ and C₇₈.

TABLE 9 HPLC analysis result composition C₇₀ (%) C₇₆ (%) C₇₈ (%) Initialfullerene mixture 7.2 52.5 40.3 Isolated fullerene mixture 3.9 44.8 51.3

In light of the foregoing, various CTV hosts can form complexes orhemicarceplexes with various fullerenes. The hemicarceplexes offullerene⊙CTV may be used to isolate a fullerene or a fullerene mixturewithin a certain steric size range from a fullerene mixture, withoutusing HPLC or recrystallization techniques. The most remarkable is thatCTV1 may be used to isolate C₇₀ in high purity (≧99.0%) from acommercial fullerene extract.

The preparation of hemicarcerands that isolate C₇₀ and higher fullerenessuggests the possibility of not only isolating and stabilizing thesenovel molecules, their analogues, and derivatives but also applying thempractically as useful photovoltaic materials by significantly increasingtheir solubility in less-polar solvents without covalently disruptingtheir unique pi-surfaces. Moreover, by elongating or shortening thelinking spacers of the CTV hosts, selective trapping of fullerenes withvarious sizes and the possibility of using them as photovoltaicmaterials are allowed.

All the features disclosed in this specification (including anyaccompanying claims, abstract, and drawings) may be replaced byalternative features serving the same, equivalent or similar purpose,unless expressly stated otherwise. Thus, each feature disclosed is oneexample only of a generic series of equivalent or similar features.

What is claimed is:
 1. A fullerene⊙CTV complex formed by trapping afullerene guest or a derivative thereof (abbreviated as a guest moleculebelow) in a cyclotriveratrylene-based molecular cage (abbreviated as CTVbelow) having a chemical structure below:

wherein LS1 and LS2 are first and second linking spacers respectivelyhaving a first chain length and a second chain length, and the firstchain length is shorter or equal to the second chain length, wherein thefirst chain length of the first linking spacers determines an interiorspace of the CTV cage for accommodating the guest molecule, and thesecond chain length of the second linking spacers determines an openingsize of the CTV cage for entering the guest molecule.
 2. The complex ofclaim 1, wherein the first linking spacers or the second linking spacersare straight alkyl chains containing at least 10 carbons foraccommodating a guest molecule having at least 60 atoms in the CTV. 3.The complex of claim 1, wherein the first linking spacers or the secondlinking spacers are straight alkyl chains containing 10-15 carbons foraccommodating the guest molecule having 60-84 carbons in the CTV.
 4. Thecomplex of claim 3, wherein the cyclotriveratrylene-based molecular cageis


5. The complex of claim 4, wherein the complex is C₆₀⊙CTV1, C₇₀⊙CTV1,C₇₆⊙CTV1, C₇₈⊙CTV1, C₆₀⊙CTV2, C₇₀⊙CTV2, C₆₀⊙CTV3, Sc₃N@Cs₈₀⊙CTV4,C₆₀⊙CTV5, C₇₀⊙CTV5, C₇₆⊙CTV5 or C₇₈⊙CTV5, C₆₀⊙CTV6, C₇₀⊙CTV7, C₇₆⊙CTV7,C₇₈⊙CTV7, C₈₂⊙CTV7, C₈₄⊙CTV7, C₈₆⊙CTV7, C₇₀⊙CTV8, C₇₆⊙CTV8, C₇₈⊙CTV8,C₈₂⊙CTV8, C₈₄⊙CTV8, C₈₆⊙CTV8, C₇₀⊙CTV9, C₆₀⊙CTV1, or C₆₀⊙CTV12.
 6. Thecomplex of claim 1, wherein at least one of the first and the secondlinking spacers containing a diester linkage.
 7. The complex of claim 6,wherein the cyclotriveratrylene-based molecular cage is


8. The complex of claim 7, wherein the complex is Sc₃N@C₈₀⊙CTV4,C₆₀⊙CTV5, C₇₀⊙CTV5, C₇₆⊙CTV5 or C₇₈⊙CTV5, or C₆₀⊙CTV6.
 9. A method offorming a fullerene⊙CTV hemicarceplex, the method comprising: mixing afullerene or a derivative thereof (abbreviated as a guest moleculebelow), and a cyclotriveratrylene-based molecular cage (abbreviated asCTV below) in a solvent to form a mixture solution, wherein the CTV hasa chemical structure shown below, and LS1 and LS2 are first and secondlinking spacers.


10. The method of claim 9, wherein the first or the second linkingspacers are straight alkyl chains containing at least 10 carbons foraccommodating a guest molecule having at least 60 atoms in the CTV. 11.The method of claim 9, wherein at least one of the first and the secondlinking spacers containing a diester linkage.
 12. The method of claim 9,wherein the solvent majorly contains CS₂, CH₂Cl₂, CHCl₃ or CHCl₂CHCl₂.13. The method of claim 9, further comprising heating the mixturesolution to form a fullerene⊙CTV hemicarceplex.
 14. The method of claim13, wherein the mixture solution is heated at a temperature above roomtemperature to 80° C.
 15. A method of isolating at least a fullerene byusing a fullerene⊙CTV hemicarceplex, the method comprising: forming atleast the fullerene⊙CTV hemicarceplex by mixing a mixture of fullerenesor derivatives thereof (abbreviated as a guest molecules below), and acyclotriveratrylene-based molecular cage (abbreviated as CTV below) in afirst solvent, wherein the first solvent has less tendency than thefullerenes to occupy an inner space of the cyclotriveratrylene-basedmolecular cage, and wherein the CTV has a chemical structure shownbelow, and LS1 and LS2 are first and second linking spacers;

isolating the fullerene⊙CTV hemicarceplex by column chromatography anddissociating the fullerene⊙CTV hemicarceplex in a second solvent,wherein the second solvent can dissolve the fullerene⊙CTV hemicarceplexand allow dissociating the fullerene⊙CTV hemicarceplex to releasefullerene.
 16. The method of claim 15, wherein the first or the secondlinking spacers are straight alkyl chains containing at least 10 carbonsfor accommodating a guest molecule having at least 60 atoms in the CTV.17. The method of claim 15, wherein at least one of the first and thesecond linking spacers containing a diester linkage.
 18. The method ofclaim 15, wherein the first solvent majorly contains CS₂, CH₂Cl₂, CHCl₃,or CHCl₂CHCl₂.
 19. The method of claim 15, wherein the second solventmajorly contains CS₂, CH₂Cl₂, CHCl₃, CHCl₂CHCl₂, benzene, toluene, ordichlorobenzene.